Thermoplastic resin compositions comprising polyphenylene ether, polyolefins and dinitrodiamines

ABSTRACT

A thermoplastic resin composition which comprises 100 parts by weight of a composition comprising 95-5 % by weight of at least one polyolefinresin (A) selected from homopolymers of ethylene or α-olefin or copolymers thereof and these homopolymers or copolymers modified with a polyfunctional compound (E) and/or an unsaturated monomer (L) and 5-95 % by weight of at least one polyphenylene-ether-resin (B) selected from polyphenylene ether, modified polyphenylene ether with the above (E) and/or (L) and a composition comprising the polyphenylene or modified polyphenylene ether and an aromatic vinyl polymer resin (M) and 0.001-10 parts by weight of a dinitrodiamine (D) of the following formula (I). ##STR1## (wherein X represents a divalent chain aliphatic group, a cyclic aliphatic group or an aromatic group which may contain a halogen or an oxygen atom, R 1  represents a hydrogen atom, a chain aliphatic group, a cyclic aliphatic group or an aromatic group and when both of X and R 1  are chain aliphatic groups, the nitrogen atoms may further bond each other to form a ring through X and R 1  ; R 2  and R 3  are independently a hydrogen atom or an alkyl group of 1-12 carbon atoms and R 2  and R 3  may bond to form a ring).

This is a divisional of application 07/667,408 which was filed on Apr.8, 1991, now U.S. Pat. No. 5,300,568, which is the PCT U.S. nationalphase application of PCT JP90/00759, filed Jun. 11, 1990.

TECHNICAL FIELD

The present invention relates to a resin composition which can beutilized as shaped article, sheet, etc. by injection molding, extrusionmolding, blow molding, etc.

More particularly, it relates to a resin composition which comprises apolyolefin and a polyphenylene ether and which is excellent in balanceof mechanical strengths and chemical resistance.

BACKGROUND ART

Since polyolefin is excellent in processability, toughness, waterresistance, organic solvent resistance and chemical resistance and islow in specific gravity and inexpensive, it has been widely utilized asvarious molded articles, films and sheets for a long time.

However, polyolefin is generally not so high in heat resistance andstiffness and is required to be further improved in these properties fornew uses.

On the other hand, polyphenylene ether has excellent heat resistance andstiffness, but: has difficulties in processability and solventresistance and thus is limited in scope of utilization thereof. In orderto improve the processability and impact strength, blend with a styreneresin is utilized, but is inferior in solvent resistance and is limitedin scope of use. For example, it is not suitable in the fields whichrequire resistance to oily solvent such as gasolin containers.

Various blend composition have been proposed for utilizing merits ofpolyolefin and polyphenylene ether and supplementing their defects andtheere is a composition for improvement of processability and tensilestrength (Japanese Patent Kokoku No. 42-7069), but this composition doesnot necessarily satisfy relatively high level of mechanical strengthrequired in industrial fields. Furthermore, in order to improvecompatibility of polyolefin and polyphenylene ether to increasemechanical strength, there were proposed compositions which contain ablock copolymer of styrene and butadiene or hydrogenation productthereof (Japanese Patent Kokai Nos. 53-71158, 54-88950 and 59-100159)and Compositions which additionally contain inorganic filler (JapanesePatent Kokai No. 58-103556). According to these proposals,processability and mechanical strength can be improved, but organicsolvent resistance possessed by polyolefin is not sufficiently exhibitedbecause addition amount of polyolefin is small or matrix (continuousphase) comprises polyphenylene ether or combination of polyphenyleneether with styrene resin. Furthermore, a composition which comprisespolyphenylene ether to which is added polyolefin in a large amount ofmore than 20% by weight and is further added a diblock copolymer orradial teleblock copolymer comprising alkenyl aromatic compound havingcompatibilizing action and conjugated diene or hydrogenation product ofthese copolymers is disclosed in Japanese Patent Kokai NOs. 58-1.03557and 60-76547. Moreover, there are disclosed. a technique of graftingstyrene compound on polyolefin and then adding thereto polyphenyleneether in Japanese Patent Kokoku No. 56-22544 and a technique of blendingpolyolefin copolymerized with glycidyl methacrylate or the like withpolyphenylene ether in Japanese Patent Kokai Nos. 57-108153 and 58-225150. In addition, there are disclosed a technique of blendingpolyphenylene ether with both a polymer having glycidyl group andpolyolefin having a group capable of reacting with glycidyl group inJapanese Patent Kokai No. 60-260449, a technique of blendingpolyphenylene ether with a modified copolymer obtained by polymerizingstyrene compound with copolymer of glycidyl (meth)acrylate and olefin inJapanese Patent Kokai No. 61-47745, and a technique of blending modifiedpolyphenylene ether and modified polyolefin with a binder having aspecific structure in Japanese Patent Kokai No. 63-128056.

However, according to these conventional techniques, compatibilitybetween polyphenylene ether and polyolefin is not necessarilysatisfactory and as a result improvement of solvent resistance andmechanical strength is not sufficient and practically satisfactorymaterials have not yet been obtained.

DISCLOSURE OF INVENTION

Under the above circumstances, the present invention aims at developingnovel additives, thereby to obtain a resin composition which contains apolyolefin-resin and a polyphenylene-ether-resin and which possessessimultaneously sufficient solvent resistance, high balance of mechanicalstrength and high processability.

As a result of research conducted by the inventors on variouspolyolefins, polyphenylene ethers and various additive components inorder to offset and improve unsatisfactory points of mechanicalproperties on conventional polyolefin-polyphenylene ether blends, it hasbeen found that a resin composition improved in compatibility betweenpolyolefin and polyphenylene ether and excellent in balance ofmechanical properties including mainly impact strength and in solventresistance. Thus, the present invention has been accomplished.

That is, the present invention relates to:

(1) A thermoplastic resin composition, characterized by comprising 95-5%by weight of a polyolefin-resin (A), 5-95% by weight of apoly-phenylene-ether-resin (B), and 0.001-10 parts by weight of adinitrodiamine (D) per 100 parts by weight of (A)+(B), wherein (A), (B)and (D) are as shown below:

(A): at least one selected from polyolefins selected from homopolymersof ethylene or α-olefin and copolymers comprising two or more of thesemonomers and modified polyolefins obtained[by modifying thesepolyolefins with modifiers in the presence or absence of radicalinitiators,

said modifier is at least one selected from polyfunctional compounds (E)having in molecule at least one of a carboxylic acid group, an acidanhydride group, an acid amide group, an imide group, a carboxylic acidester group, an epoxy group, an amino group and a hydroxyl group andunsaturated monomers (L) other than the polyfunctional compounds (E).

(B): at least one selected from polyphenylene ethers, modifiedpolyphenylene ethers obtained by modifying polyphenylene ethers with theabove modifier in the presence or absence of a radical initiator,compositions comprising a polyphenylene ether and at least one aromaticvinyl polymer resin (M) selected from aromatic vinyl polymers,copolymers of aromatic vinyl compound with other monomers andrubber-modified aromatic vinyl polymers and compositions comprisingmodified polyphenylene ether and at least one aromatic vinyl polymerresin (M).

(D): Dinitrodiamines represented by the formula (I): ##STR2## (wherein Xrepresents a divalent chain aliphatic group, a cyclic aliphatic group oran aromatic group which may contain a halogen or an oxygen atom; R¹represents a hydrogen atom, a chain aliphatic group, a cyclic aliphaticgroup or an aromatic group and when both of X and R¹ are chain aliphaticgroups, nitrogen atoms may further bond each other to form a ringthrough X and R¹ ; and R² and R³ are independently a hydrogen atom or analkyl group of 1-12 carbon atoms and R² and R³ may bond to form a ring).

(2) A thermoplastic resin composition, characterized by comprising 94-2%by weight of a polyolefin-resin (A), 2-94% by weight of apolyphenylene-ether-resin (B), 1-50% by weight of a rubber-like material(C), and 0.001-10 parts by weight of a dinitrodiamine (D) per 100 partsby weight of (A)+(B)+(C), wherein (C) is as shown below:

(C): at least one of natural or synthetic elastomeric polymers which areelastic at 20°-25° C and modified elastomeric polymers obtained bymodifying these elastomeric polymers with modifier mentioned in (1) inthe presence or absence of a radical initiator.

Further, the present invention will be specifically explained based onembodiments. That is, the present invention relates to:

(3) A thermoplastic resin composition mentioned in (1) which is preparedby adding 0.001-10 parts by weight of dinitrodiamine (D) to 100 parts byweight of a composition (R-1) comprising 95-5% by weight ofpolyolefin-resin (A) and 5-95% by weight of polyphenylene-ether-resin(B),

(4) A thermoplastic resin composition mentioned in (2) which is preparedby adding 0.001-10 parts by weight of dinitrodiamine (D) to 100 parts byweight of a composition (R-2) comprising 94-2% by weight of thepolyolefin-resin (A), 2-94% by weight of the polyphenylene-ether-resin(B) and 1-50% by weight of rubber-like material (C),

(5) A thermoplastic resin composition mentioned in (1) or (2) which isprepared by further adding 1-1800 parts by weight of polyolefin and/or1-100 parts by weight of elastomeric polymer to 100 parts by weight ofthe thermoplastic resin composition mentioned in (3), amount ofsaidpolyolefin being less than 95% by weight based on the total amountof this polyolefin and the polyolefin-resin (A) in composition (R-1),

(6) A thermoplastic resin composition mentioned in (2) which is preparedby further adding 1-1800 parts by weight of polyolefin and/or 1-100parts by weight of elastomeric polymer to 100 parts by weight of thethermoplastic resin composition mentioned in (4), amount of saidpolyolefin being less than 95% by weight based on the totell amount ofthis polyolefin and the polyolefin-resin (A) in the composition (R-2)and amount of said elastomeric polymer being less than 95% by weightbased on the total amount of this elastomeric polymer and therubber-like material (C) in the composition (R-2),

(7) A thermoplastic resin composition mentioned in (1) which is preparedby adding 0.01-20 parts by weight of a polyfunctional compound (E)containing 0.01-20 parts by weight of an unsaturated monomer (L) or not,and 0.001-10 parts by weight of a radical initiator to 100 parts byweight of the composition (R-1) mentioned in (3) and melt kneading themixture to obtain the composition (R-3) and adding 0.001-10 parts byweight of dinitrodiamine (D) to 100 parts by weight of the composition(R-3),

(8) A thermoplastic resin composition mentioned in (2) which is preparedby adding 0.01-20 parts by weight of a polyfunctional compound (E)containing 0.01-20 parts by weight of an unsaturated monomer (L) or not,and 0.001-10 parts by weight of a radical initiator to 100 parts byweight of the composition (R-2) mentioned in (4), melt kneading themixture to obtain a composition (R-4), and adding 0.001-10 parts byweight of dinitrodiamine (D) to 100 parts by weight of the composition(R-4),

(9) A thermoplastic resin composition mentioned in (1) or (2) which isprepared by adding 0.01-20 parts by weight of a polyfunctional compound(E) containing 0.01-20 parts by weight of an unsaturated monomer (L) ornot, and 0.001-10 parts by weight of a radical initiator to 100 parts byweight of the composition (R-1 ) mentioned in (3 ), melt kneading themixture to obtain the composition (R-3), and adding 0.001-10 parts byweight of dinitrodiamine (D) and 1-1800 parts by weight of polyolefinand/or 1-100 parts by weight of elastomeric polymer, amount of saidpolyolefin being less than 95% by weight based on the total amount ofthis polyolefin and the polyolefin-resin (A) in the composition (R-1),

(10) A thermoplastic resin composition mentioned in (2) which isprepared by adding 0.001-20 parts by weight of a polyfunctional compound(E) containing 0.01-20 parts by weight of an unsaturated monomer (L) ornot, and 0.001-10 parts by weight of a radical initiator to 100 parts byweight of the composition (R-2) mentioned in (4), melt kneading themixture to obtain a composition (R-4), and adding 0.001-10 parts byweight of dinitrodiamine (D) and 1-1800 parts by weight of polyolefinand/or 1-100 parts by weight of elastomeric polymer to 100 parts byweight of said composition (R-4), amount of said polyolefin being lessthan 95% by weight based on the total amount of this polyolefin and thepolyolefin-resin (A) in the composition (R-2) and amount of saidelastomeric polymer being less than 95% by weight based on the totalamount of this elastomeric polymer and, the rubber-like material (C) inthe composition (R-2), and

(11) A thermoplastic resin composition mentioned in (1) or (2), whereinthe polyolefin is at least one crystalline polypropylene selected fromcrystalline propylene homopolymers, crystalline propylene/α-olefinrandom copolymers prepared by copolymerizing propylene with 6 mol % orless of ethylene and/or at least one other α-olefin, and crystallinepropylene/α-olefin block copolymer having propylene homopolymer portionor propylene/α-olefin random copolymer portion containing 6 mol % orless of ethylene and/or at least one other α-olefin, as the firstsegment, and propylene/α-olefin random copolymer portion containing 10mol % or more of ethylene and/or at least one other α-olefin, as thesecond segment.

The polyolefin-resin (A) is at least one selected from polyolefinsselected from homopolymers of ethylene or α-olefin and copolymers of twoor more of these monomers and modified polyolefins obtained by modifyingthese polyolefins with a modifier in the presence or absence of radicalinitiator.

Polyolefins are crystalline olefin polymers and, as examples thereof,mention may be made of polymers of olefins per se such as polypropylene,high-density polyethylene, low-density polyethylene, linear low-densitypolyethylene, propylene-ethylene copolymer, ethylene-butene-1 copolymer,ethylenepentene copolymer, ethylene-hexene copolymer, andpoly-4-methylpentene-1; and copolymers of a major amount of olefin andvinyl monomer copolymerizable therewith (for example, acrylic esters,methacrylic esters, vinyl acetate, styrene, acrylonitrile, and glycidyl(meth)acrylate). Copolymerization may be any of random copolymerization,block copolymerization, and graft copolymerization. These may be usedsingly or as a mixture of two or more. Among these polyolefins,polyethylene and polypropylene are preferred and polypropylene andrandom copolymers and block copolymers of propylene-ethylene areespecially preferred.

These polyolefins can be prepared by processes known to one skilled inthe art, for example, one mentioned in "ENCYCLOPEDIA OF POLYMER SCIENCEAND TECHNOLOGY", vol. 6, page 275 (1967) and vol. 11, page 597 (1969)published from John Wiley & Sons, inc.

Polypropylene in the present invention is crystalline polypropylene andincludes, in addition to the crystalline propylene homopolymer,crystalline propylene/α-olefin block copolymers obtained by polymerizingpropylene or copolymerizing propylene and 6 mol % or less of ethyleneand/or at least one other α-olefin such as butene-1 at the first stepand copolymerizing propylene and 10 mol % or less of ethylene and/or atleast one other α-olefin such as butene-1 at the second step, andcrystalline propylene/α-olefin random copolymers obtained bycopolymerizing propylene with 6 mol % or less of ethylene and/or atleast one other α-olefin such as butene-1 and hexene-1.

Crystalline polypropylene can be obtained by carrying out reaction inthe presence of a catalyst comprising a combination of titaniumtrichloride and an alkylaluminum compound which is usually calledZiegler-Natta catalyst.

Polymerization can be carried out at 0° C.-300° C. However, in the caseof highly stereoregular polymerization of α-olefins such as propylene,the polymerization is suitably carried out at 0° C.-100° C. becausehighly stereoregular polymer cannot be obtained at a temperature higherthan 100° C.

Polymerization pressure has no special limitation, but apressure ofabout 3-100 atm is desired from industrial and economical viewpoints.

Polymerization method may be either continuous type or batch type.

Polymerization method may be slurry polymerization using inerthydrocarbon solvents such as butane, pentane, hexane, heptane andoctane, solvent polymerization according to which polymerization iscarried out at the state where produced polymer is dissolved in theinert hydrocarbon solvents, bulk polymerization in liquefied monomerwith no solvents, and gas phase polymerization in gaseous monomer.

It is also possible to add a chain transfer agent such as hydrogen-formodification of molecular weight of polymer.

Crystalline polypropylene used in the present invention can be preparedby using isospecific Ziegler-Natta catalyst. Catalyst used is preferablyhigh in isospecificity.

Catalysts which can be suitably used are those which comprise titaniumtrichloride having layer crystal structure or a composite solid compoundof a magnesium compound and a titanium compound as a transition metalcatalyst component and an organo-aluminum compound as typical metalcomponent. The catalysts can contain known electron donating compound asa third component.

As titanium trichloride, there may be used one which is prepared byreducing titanium tetrachloride with various reducing agents. Metalssuch as aluminum and titanium, hydrogen, organometallic compounds areknown as the reducing agents. Typical example of titanium trichlorideprepared by reduction with metal is a titanium trichloride composition(TiCl₃ AA) containing chloride of aluminum obtained by reducing titaniumtetrachloride with metallic aluminum and then activated by grinding inball mills, vibration mills, and the like. In order to improveisospecificity, polymerization activity and/or particle properties, acompound selected from ether, ketone, ester, aluminum chloride, titaniumtetrachloride and the like may be allowed to coexist at the time ofgrinding.

Titanium trichloride more preferred for the object of the presentinvention is one which is obtained by reducing titanium tetrachloridewith an organoaluminum compound and subjecting the resulting titaniumtrichloride composition to catalytic reaction with an ether compound anda halogen compound simultaneously or successively. The ether compound ispreferably one which has the formula R¹ -O-R² (R¹, R² are alkyl groupsof 1-18 carbon atoms), and especially preferred are di-n-butyl ether anddi-t-amyl ether. Halogen is especially preferably iodine, halogencompound is especially preferably iodine trichloride, titanium halide isespecially preferably titanium tetrachloride, and halogenatedhydrocarbons are especially preferably carbon tetrachloride and1,2-dichloroethane. Organoaluminum compounds are preferably those whichare represented by the formula AlR³ X_(3-n) (R³ is a hydrocarbon groupof 1-18 carbon atoms, X is a halogen selected from Cl, Br, and I and nis a numeral satisfying 3≧n>1) and especially preferably diethylaluminumchloride and ethylaluminum sesquichloride.

Processes for preparing these titanium trichlorides are mentioned indetail in Japanese Patent Kokai Nos. 47-34470, 53-33289, 53-51285,54-11986, 58-142903, 60-28405, 60-228504, and 61-218606.

When titanium trichloride having a layer crystal structure is used as atransition metal compound component, an organoaluminum compoundrepresented by the formula AlR⁴ _(m) X₃₋₃₁ m (R⁴ is a hydrocarbon groupof 1-18 carbon atoms, X is a halogen selected from Cl, Br and I, and mis 3≧m>0) is preferred as a typical metal compound component.Organoaluminum compounds especially preferred for attaining the objectof the present invention are those which have an ethyl or isobutyl groupas R⁴ with m being 2.5≧m>1.5. Examples are diethylaluminum chloride,diethylaluminum bromide, diethylaluminum iodide and mixtures thereofwith triethylaluminum or ethylaluminum dichloride. When a thirdcomponent mentioned hereinafter is used in combination, organoaluminumcompounds of 3≧m>2.5 or 1.5≧m>0 can also be suitably used for attainingthe object of the present invention.

Ratio of organoaluminum compounds and titanium trichloride can beselected from the wide molar ratio range of 1:1-1000:1.

Catalyst comprising titanium trichloride and organoaluminum compound cancontain known the third component. As the third component, mention maybe made of, for example, ester compounds such as ε-caprolactam, methylmethacrylate, ethyl benzoate, and methyl toluylate, phosphite esterssuch as triphenyl phosphite and tributyl phosphite, and phosphoric acidderivatives such as hexamethyl-phosphorictriamide.

Amount of the third component used must be determined experimentally forevery compound because respective compounds differ in action, but ingeneral the amount is at most equimolar to the organoaluminum compound.

When composite solid compounds of magnesium compounds and titaniumcompounds are used as a transition metal solid catalyst component,organoaluminum compounds, especially those which are represented by theformula AlR⁵ _(p) X_(3-p) (R⁵ is a hydrocarbon group of 1-18 carbonatoms, X is a halogen selected from Cl, Br and I and p is 3≧p>2) arepreferred. Examples of them are triethylaluminum, triisobutylaluminum,and mixtures thereof with diethylaluminum chloride or diisobutylaluminumchloride.

The catalyst preferably contains an electron donating compound,especially an aromatic monocarboxylate ester and/or silicone compoundhaving Si-OR⁶ bond.

As silicone compounds having Si-OR⁶ bond (R⁶ is a hydrocarbon group of1-20 carbon atoms), suitable are alkoxysilane compounds represented bythe formula R⁷ _(a) Si(OR⁶)_(4-a) (R⁶ and R⁷ each represents ahydrocarbon group of 1-20 carbon atoms and a is 0≦a≦3). As examplesthereof, mention may be made of tetramethoxysilane,methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane,phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane, butyltriethoxysilane,tetrabutoxysilane, vinyltributoxysilane and diethyldiethoxysilane.

The electron donating compound is preferably used in an amount withinthe range of 1 mol or less, especially 0.05-1 mol per 1 mol of theorganoaluminum compound.

As composite solid compounds of magnesium compounds and titaniumcompounds, there may be used titanium trichloride containing chloride ofmagnesium which is obtained by reducing titanium tetrachloride with anorganomagnesium compound or so-called "supported catalyst" prepared bycatalytic reaction of a solid magnesium compound with a liquid phasetitanium compound. The solid magnesium compound preferably containselectron donating compounds, especially aromatic monocarboxylate esters,aromatic dicarboxylate diesters, ether compounds, alcohols and/orphenols. The aromatic monocarboxylate ester may be allowed to coexist atthe time of catalytic reaction with titanium compounds.

The above composite solid compounds of magnesium compounds and titaniumcompounds are disclosed in many patent publications and catalystssuitable for attaining the objects of the present invention arementioned in detail in Japanese Patent Kokai Nos. 54-112988, 54-119586,56-30407, 57-59909, 57-59910, 57-59911, 57-59912, 57-59914, 57-59915,57-59916, 54-112982, 55-133408 and 58-27704.

When the thermoplastic resin composition of the present invention isemployed for uses which require heat resistance, stiffness andscratchability, it is preferred to use, as crystalline polypropylene, ahighly crystalline polypropylene wherein isotactic pentad ratio in aboiling heptane-insoluble fraction of the crystalline propylenehomopolymer or of the propylene homopolymer portion which is the firstsegment polymerized in the first step for the crystallinepropylene/α-olefin block copolymer is 0.970 or more and a content of aboiling heptane-soluble fraction is 5.0% by weight or less and a contentof a 20° C. xylene-soluble fraction is 2.0% by weight or less.

The isotactic pentad ratio in the boiling heptane-insoluble fraction,the content of boiling heptane-soluble fraction and the content ofpolymer soluble in xylene of 20° C. mentioned above are determined inthe following manner.

Five g of crystalline polypropylene is completely dissolved in 500 ml ofxylene and then the solution is cooled to 20° C. and is left to standfor 4 hours. Thereafter, this is filtered to remove the: 20° C.xylene-insoluble fraction. The filtrate is concentrated to dryness toevaporate xylene and further dried at 60° C. under reduced pressure toobtain the polymer soluble in xylene of 20° C. Dry weight of thispolymer is divided by weight of a charged sample and the resulting valueexpressed by percentage is the content of 20° C. xylene-solublefraction. The 20° C. xylene-insoluble fraction is dried and then issubjected to Soxhlet extraction with boiling n-heptane for 8 hours. Theextraction residue is called the boiling heptane-insoluble fraction.Value obtained by subtracting dry weight of this boilingheptane-insoluble fraction from weight of the charged sample (5 g) isdivided by weight of the charged sample. The thus obtained valueexpressed by percentage is the content of boiling heptane-solublefraction.

Isotactic pentad ratio is an isotactic chain as pentad unit incrystalline polypropylene molecular chain, in other words, proportion ofpropylene monomer unit present at the center of chain formed bysuccessive five propylene monomer units having four meso-linkages whichis measured by the method disclosed by A. Zambelli et al in"Macromolecules", 6,925 (1973), namely, by using ¹³ C-NMR. Assignment ofNMR absorption. peak is carried out based on the subsequently published"Macromolecules", 8, 687 (1975).

Specifically, isotactic pentad ratio is measured as an area proportionof mmmm peak in all absorption peaks of a methyl carbon region of ¹³C-NMR spectrum. Isotactic pentad ratio of a NPL standard substance CRMNo. M19-14 Polypropylene PP/MWD/2 manufactured by National PhysicalLaboratory, England, is 0.944 according to the above method.

The highly crystalline polypropylene can be prepared by the processesexemplified in Japanese Patent Kokai Nos. 60-28405, 60-228504, 61-218606and 61-287917.

When the thermoplastic resin composition of the present invention isemployed for uses which require impact resistance, the crystallinepolypropylene is preferably a crystalline propylene/α-olefin blockcopolymer which comprises a propylene homopolymer portion or apropylene/α-olefin random copolymer portion which is the first segmentpolymerized in the first step and a propylene/α-olefin random copolymerportion which is the second segment polymerized in the second step.

The block copolymer can be produced by slurry polymerization process andgas phase polymerization process. When it is used for use which requiresespecially high impact resistance, it is necessary to increase amount ofthe second segment and such block copolymer can be produced suitably bygas phase polymerization process.

The high-impact polypropylene according to gas phase polymerizationprocess can be produced, for example, by the process disclosed inJapanese Patent Kokai No. 61-287917.

The first segment of the block copolymer preferably has a propylenehomopolymer portion or a propylene/α-olefin random copolymer portioncontaining at most 6 mol % of ethylene and/or at least one otherα-olefin.

The second segment preferably has an ethylene homopolymer portion, or apropylene/α-olefin random copolymer portion containing at least 10 mol %of ethylene or at least one other α-olefin, or a random copolymerportion of ethylene and propylene having ethylene content of at least 10mol %, or a random copolymer portion of propylene and ethylene with orwithout α-olefins of 4-6 carbon atoms which has an ethylene content ofat least 10 mol %. The second segment is in an amount of 10-70% byweight based on total polymerization amount.

In case of slurry polymerization process, the block copolymer isproperly produced with the second segment amount being within the rangeof 10-30% by weight and in case of gas phase polymerization process, itis properly produced with the second segment amount being within therange of 10-70% by weight.

In case of gas phase polymerization process, propylene block copolymerof the larger second segment amount can be produced by the processmentioned in Japanese Patent Application No. 62-256015 and this can besuitably applied to the use which requires superhigh impact resistance.

Intrinsic viscosity of the second. segment in tetralin solvent at 135°C. must be changed depending on productivity at preparation, powderproperties of polymer and intrinsic viscosity of the first segment, butis normally 3-8 dl/g in case of slurry polymerization process and 1-5dl/g in case of gas phase polymerization process.

The modified polyolefin used in the present invention is a polyolefinwhich is modified with at least one modifier selected frompolyfunctional compounds (E) having, in molecule, at least one of acarboxylic acid group, an acid anhydride group, an acid amide group, animide group, a carboxylic acid ester group, an epoxy group, an aminogroup and a hydroxyl group and unsaturated monomers (L) other than thepolyfunctional compounds (E) in the presence or absence of a radicalinitiator. These modifiers and amount thereof will be explainedspecifically in the part of explanation about process for production ofmodified polyphenylene ether.

As process for production of modified polyolefin, known processes can beemployed and specifically, the processes mentioned in the part aboutprocess for production of modified polyphenylene ether are used.

In the present invention, as one preferred embodiment of modifiedpolypropylene among modified polyolefins, it can be obtained by graftcopolymerizing polypropylene with an unsaturated carboxylic acid or aderivative thereof as a modifier (hereinafter referred to as "graftmonomer"), preferably together with an aromatic vinyl monomer and, ifnecessary, in the presence of a radical initiator. A process forproduction of the modified polypropylene will be specifically explained.

A modified polypropylene which is large in grafting amount ofunsaturated carboxylic acid or derivative thereof, is less in change offlowability (melt flow rate) before and after graft modification and isexcellent in properties can be obtained by graft modification in thepresence of aromatic vinyl monomers.

For grafting the graftable monomer on polypropylene, various knownprocesses carl be employed.

That is, there are a process which comprises mixing polypropylene, agraftable monomer and a radical initiator and melt kneading the mixturein a melt kneading apparatus to perform grafting, a process whichcomprises dissolving polypropylene in an organic solvent such as xylene,then carrying out a reaction by heating with addition of radicalinitiators under stirring in nitrogen atmosphere, cooling the reactionmixture after completion of the reaction, washing and flitrating it,followed by drying to obtain grafted polypropylene, a process whichcomprises irradiating polypropylene with ultraviolet ray or radiation inthe presence of graftable monomer and a process which comprisescontacting polypropylene with oxygen or ozone.

Most preferred is the process which comprises graft copolymerizing bymelt kneading in a melt kneading apparatus from economical viewpoint.

Polypropylene, an unsaturated carboxylic acid or derivative thereof andan unsaturated aromatic monomer and, if necessary, a radical initiatorcan be melt kneaded at a temperature of 150°-300° C., preferably190°-280° C. and for a residence time of 0.3-10 minutes, preferably0.5-5 minutes using an extruder, Banbury mixer, kneader or the like.Industrially advantageous process is one which is carried outcontinuously by single-screw or twin-screw extruders with keeping ventholes at vacuum state and with removing unaltered components(unsaturated carboxylic acids or derivative thereof, unsaturatedaromatic monomers, radical initiators) and side-reaction products suchas oligomer and decomposition products. Reaction atmosphere may be air,but preferably inert gas such as nitrogen or carbon dioxide. Theresulting modified polypropylene may be further subjected to a heattreatment at higher than 60° C., solvent extraction and drawing a vacuumin melting for further removing slight amounts of unaltered componentsand side-reaction products contained in the modified polypropylene.

Furthermore, if necessary, various additives such as antioxidant, heatstabilizer, light stabilizer, nucleating agent, lubricant, antistaticagent, inorganic or organic colorant, rust preventive, crosslinkingagent, foaming agent, plasticizer, fluorescent agent, surface smoothingagent, and surface gloss improver can be added to the modifiedpolypropylene during production step or subsequent processing steps.

As the unsaturated carboxylic acids or derivatives thereof used formodification of polypropylene, mention may be made of, for example,unsaturated carboxylic acids such as acrylic acid, methacrylic acid,maleic acid, itaconic acid, citraconic acid, himic acid,bicyclo(2,2,2)octa-5-ene-2,3-dicarboxylic acid,4-methylcyclohexa-4-ene-1,2-dicarboxylic acid,1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo(2,2,1) octa-7-ene-2,3,5,6-tetracarboxylic acid, and 7-oxabicyclo(2,2,1)hepta-5-ene-2,3-dicarboxylic acid. As derivatives of unsaturatedcarboxylic acids, there are acid ahydrides, esters, amides, imides andmetal salts such as, for example, maleic anhydride, itaconic anhydride,citraconic anhydride, himic anhydride, monoethyl maleate, monomethylfumarate, monomethyl itaconate, dimethyl fumarate, dimethylaminoethylmethacrylate, dimethylaminopropylacrylamide, acrylamide, methacrylamide,maleic acid monoamide, maleic acid diamide, maleicacid-N-monoethylamide, maleic acid-N, N-diethylamide, maleicacid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acidmonoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaricacid-N,N-diethylamide, fumaric acid-N-monobutylamide, fumaricacid-N,N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide,sodium acrylate, sodium methacrylate, potassium acrylate, and potassiummethacrylate.

Among them, use of maleic anhydride is most preferred.

As the aromatic vinyl monomers used for the modified polypropylene,styrene is most preferred, but o-methylstyrene, p-methylstyrene,m-methylstyrene, α-methylstyrene, vinyltoluene, and divinylbenzene mayalso be used and these may also be used in admixture.

Production of the modified polypropylene can also be carried out in theabsence of a radical initiator, but is usually preferably carried out inthe presence of a radical initiator. As a radical initiator, there maybe used known ones and as examples, mention may be made of azo compoundssuch as 2,2'-azobisisobutyronitrile and2,2'-azobis(2,4,4)-trimethylvaleronitrile, and various organic peroxidessuch as methyl ethyl kenone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, 2,2-bis(t-butylperoxy)butane, t-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide,1,3-bis(t-butylperoxyisopropyl)benzene,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, lauroyl peroxide,3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate,t-butylperoxyisobutyrate, t-butyloxypivarate,t-butyl-oxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate,t,-butylperoxylaurate, t-butylperoxybenzoate,di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane,t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, andpolystyrene peroxide.

Melt flow rate of starting polypropylenes (crystalline propylenehomopolymer, crystalline propylene/α-olefin block copolymer crystallinepropylene/α-olefin random copolymer) in production of modifiedpolypropylene is 0.05-60 g/10 min, preferably 0.1-40 g/10 min, butdesirably is selected so that melt flow rate of the resulting modifiedpolypropylene is 0.1-100 g/10 rain, preferably 0.5-50 g/10 min. Further,number-average molecular weight of starting polypropylene is7,000-800,000, preferably 10,000-700,000.

Amounts of respective components in production of modified polypropyleneare as follows: amount of unsaturated carboxylic acid or derivativethereof is preferably 0.01-10 parts by weight, more preferably 0.1-5parts by weight, that of aromatic vinyl monomer is preferably 0.01-10parts by weight, more preferably 0.1-5 parts-by weight and that ofradical initiator is preferably 0-5 parts by weight, more preferably0.001-2 parts by weight per 1.00 parts by weight of polypropylene. Whenaddition amount of unsaturated carboxylic acid or derivative thereof isless than 0.01 part by weight, modification effect is not so high andwhen it is more than 10 parts by weight, modification effect reachessaturation and not only no further conspicuous effect is exhibited, butalso it remains much in the polymer as unaltered materials, which haveoffensive smell and causes reduction of properties and such ispractically not preferred. When addition amount of aromatic vinylmonomer is less than 0.01 part by weight, modification effect is not sohigh and when it is more than 10 parts by weight, no further conspicuouseffect can be obtained. Further, addition amount of a radical initiatorof more than 5% by weight is not practically preferred because nofurther conspicuous effect is exhibited on graft reaction of unsaturatedcarboxylic acid or derivative thereof and polypropylene decomposes muchand change in flowability (melt flow rate) is great.

The aromatic vinyl-graft polypropylenes are polypropylenes obtained bygraft copolymerizing polypropylene with aromatic vinyl monomersrepresented by the formula: ##STR3## [wherein R represents a hydrogenatom, a lower alkyl group (such as an alkyl group of 1-4 carbon atoms)or a halogen atom, Z represents a hydrogen atom, a vinyl group, ahalogen, an amino group, a hydroxyl group or a lower alkyl group, and prepresents 0 or an integer of 1-5].

As examples of aromatic vinyl monomers, mention may be made of styrene,2,4-dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene,p-divinylstyrene, p-(chloromethoxy)-styrene, α-amethylstyrene,o-methyl-α-methylstyrene, m-methyl-α-methylstyrene,p-methyl-α-methylstyrene, and p-methoxy-α-methylstyrene. These may beused singly or in combination of two or more. Among them, styrene ismost preferred.

Process for production of aromatic vinyl-graft polypropylene by graftcopolymerization of aromatic vinyl monomer has no special limitationand, for example, there may be used any known methods such as suspensionpolymerization, emulsion polymerization, solution polymerization, bulkpolymerization (including a method using extruders in addition to methodusing polymerization tanks). Specifically, there may be employed amethod mentioned in the part of explanation of modified polyphenyleneether.

Specifically, mention may be made of a method which comprises firstpreparing a polymer of aromatic vinyl monomer by anion polymerizationand then melt kneading this polymer and polypropylene together withperoxide as shown below to obtain an aromatic vinyl-graft polypropyleneand a method which comprises copolymerizing polypropylene with aromaticvinyl monomer by radical polymerization.

Peroxides used in production of the above aromatic vinyl graftpolypropylene have no special limitation and desired ones can beoptionally chosen and used. Various peroxides mentioned in the part onexplanation of modified polyphenylene ether can be referred to.

Aromatic vinyl monomer is graft copolymerized in an amount of 0.2-150parts by weight, preferably 2-90 parts by weight, more preferably 3-70parts by weight per 100 parts by weight of polypropylene.

In the present invention, polyphenylene-ether-resin (B) includes atleast one selected from polyphenylene ether, modified polyphenyleneether obtained by modifying polyphenylene ether with a modifier in thepresence or absence of radical initiator, a composition comprisingpolyphenylene ether and at least one aromatic vinyl polymer resin (M)selected from aromatic vinyl polymer, copolymer of aromatic vinylcompound and other monomer, and rubber-modified aromatic vinyl polymer,and a composition comprising modified polyphenylene ether and aromaticvinyl polymer resin (M) .

The modified polyphenylene ether in the present invention is oneobtained by modifying polyphenylene ether with at least one selectedfrom polyfunctional compound (E) and unsaturated monomer (L) other thansaid polyfunctional compound (E).

The polyphenylene ether is a polymer obtained by oxidationpolymerization of a phenol compound represented by the formula (II):##STR4## (wherein Q¹, Q², Q³, Q⁴ and Q⁵ each represents a hydrogen atom,a halogen atom, a hydrocarbon group or a substituted hydrocarbon groupand one of them is necessarily a hydrogen atom) with oxygen or a gascontaining oxygen using an oxidation coupling catalyst.

Examples of Q¹, Q², Q³, Q⁴ and Q⁵ in the above formula (II) arehydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl,butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl,carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl,methylphenyl, dimethylphenyl, and ethylphenyl.

Examples of the phenol compounds shown by the above formula are phenol,o-, m- or p-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol,2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol,2-methyl-6-ethylphenol, and 2,3,5-, 2,3,6-, and 2,4,6-trimethylphenol.These phenol compounds may also be used in combination of two or more.

Further, the polyphenylene ether may be copolymers of the phenolcompounds of the above formula and other phenol compounds, for example,dihydric phenols such as bisphenol A, tetrabromobisphenol A, resorcin,and hydroquinone. Among them, preferred are homopolymers and copolymersof 2,6-dimethylphenol and 2,3,6-trimethylphenol.

Especially preferred is poly(2,6-dimethyl-1,4-phenylene)ether.

Any oxidation coupling catalysts can be used for oxidationpolymerization of the phenol compounds as far as they havepolymerization ability. Typical example thereof are catalysts comprisingcuprous salt and tert. amine such as cuprous chloride-trimethylamine,cuprous acetate-triethylamine and cuprous chloride-pyridine; catalystscomprising cupric salt/tert. amine and alkali metal hydroxide such ascupric chloride-pyridine-potassium hydroxide; catalysts comprisingmanganese salt and primary amine such as manganese chloride-ethanolamineand manganese acetate-ethylenediamine; catalysts comprising manganesesalt and alcoholate or phenolate such as manganese chloride-sodiummethylate and manganese chloride-sodium phenolate; catalysts comprisingmanganese salt, alkali hydroxide and amine such as manganesechloride-NaOH-diethanolaminedibutylamine, manganesechloride-NaOH-triethanolaminedibutylamine and manganesechloride-NaOH-monoethanol-amine-dibutylamine, and catalysts comprisingcobalt salt and tert. amine.

Intrinsic viscosity (measured in chloroform at 30° C.) of polyphenyleneether used in the present invention has no special limitation, butpreferably is 0.2-1.0 dl/g, more preferably 0.25-0.6 dl/g and optimumintrinsic viscosity can be selected depending on circumstances.

The modifier used for preparation of modified polyphenylene ether,modified polyolefin or modified elastomeric polymer is at least oneselected from polyfunctional compound (E) having, in molecule, at leastone of a carboxylic acid group, an acid anhydride group, an acid amidegroup, an imide group, a carboxylic acid ester group, an epoxy group, anamino group, or a hydroxyl group and unsaturated monomer (L) other thanthe polyfunctional compound (E). Preferred polyfunctional compound (E)is compound (F) having in molecule simultaneously (a) carbon-carbondouble bond or carbon-carbon triple bond and (b)at least one of acarboxylic acid group, an acid anhydride group, an acid amide group, animide group, a carboxylic acid ester group, an epoxy group, an aminogroup and a hydroxyl group.

Examples of the compound (F) are maleic anhydride, maleic acid, fumaricacid, maleimide, maleic acid hydrazide, reaction products of maleicanhydride and diamine, for example, compounds having the formulas:##STR5## (wherein R is an aliphatic or aromatic group), methylnadicanhydride, dichloromaleic anhydride, maleic acid amide, natural fats andoils such as soybean oil, tung oil, caster oil, linseed oil, hempseedoil, cottonseed oil, sesame oil, rapeseed oil,.peanut oil, camellia oil,olive oil, coconut oil, and sardine oil; epoxidized natural fats andoils such as epoxided soybean oil; unsaturated carboxylic acids such asacrylic acid, butenoic acid, crotonic acid, vinylacetic acid,methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoicacid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2 hexenoic acid, 2-methyl-2-pentenoic acid,3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoicacid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoicacid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid,4-tetradecenoic acid, 9-tetradecenoic acid, 9 -hexadecenoic acid,2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoicacid, erucic acid, tetracocenoic acid, mycolipenic acid,2,4-pentadienoic acid, 2,4 -hexadienoic acid, diallylacetic acid,geranic acid, 2,4 -decadienoic acid, 2,4 -dodecadienoic acid,9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoicacid, linolic acid, linolenic acid, octadecatrienoic acid, eicosadienoicacid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid,eleostearic acid, oleic acid, eicosapentaenoic acid, erucinic acid,docosadienoic acid, docosatrienoic acid, docosatetraenoic acid,docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid,hexacodienoic acid, octacosenoic acid, and triacontenoic acid; andesters, acid ,amides and anhydrides of these unsaturated carboxylicacids; unsaturated alcohols such as allyl alcohol, crotyl alcohol,methylvinyl carbinol, allyl carbinol, methylpropenyl carbinol,4-pentene-l-ol, 10-undecene-1-ol, propargyl alcohol, 1,4-pentadiene3-ol,1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, 2,4-hexadiene-1-ol, alcoholsrepresented by the formulas C_(n) H_(2n-5) OH, C_(n) H_(2n-7) OH, C_(n)H_(2n-9) OH (n is a positive integer), 3 -butene-1,2-diol,2,5-dimethyl-3-hexene- 2,5-diol, 1,5-hexadiene-3,4-diol, and2,6-octadiene-4,5-diol and unsaturated amines such as ones where an OHgroup of these unsaturated alcohols is replaced by an -NH₂ group;moreover, low polymers such as butadiene and isoprene (e.g., 500-10,000in average molecular weight) or high polymers (e.g., at least 10000 inaverage molecular weitht) to which maleic anhydride or phenols are addedor to which an amino group, a carboxylic acid group, a hydroxyl group,an epoxy group, or the like is introduced.

Among these compounds, especially preferred is maleic anhydride.

Furthermore, mention may be made of unsaturated epoxy compounds havingan ethylenically unsaturated group and an epoxy group in molecule.

For example, mention may be made of unsaturated glycidyl esters andunsaturated glycidyl ethers represented by the following formulas (1)and (2). ##STR6## (R is a hydrocarbon group of 2-18 carbon atoms whichhas ethylenically unsaturated bond). ##STR7## (R is a hydrocarbon groupof 2-18 carbon atoms which has ethylenically unsaturated bond and X is-CH₂ --O-- or ##STR8##

Examples are glycidyl acrylate, glycidyl methacrylate, glycidylitaconate esters, allylglycidyl ether, 2-methylallylglycidyl ether, andstyrene-p-glycidyl ether.

Other preferable polyfunctional compounds (E) are compounds (G) selectedfrom aliphatic carboxylic acids, acid esters and acid amides representedby the formula: (R^(I) O)mR(COOR^(II))n(CONR^(III) R^(IV))s (wherein Rrepresents a straight chain or branched chain saturated aliphatichydrocarbon group having 2-20 carbon atoms; R^(I) represents a hydrogenatom or an alkyl, aryl, acyl or carbonyldioxy group having 1-10 carbonatoms; R^(II) represents a hydrogen atom or an alkyl or aryl grouphaving 1-20 carbon atoms; R^(III) and R^(IV) each represents a hydrogenatom or an alkyl or aryl group having 1-10 carbon atoms; m, n and s eachrepresents 0 or an integer of 1 or more and m+n+s≧2) and derivativesthereof.

Examples of the compounds (G) are hydroxy-acetic acid, lactic acid,α-hydroxy-n-butyric acid, α-hydroxyisobutyric acid, α-hydroxy-n-valericacid, α-hydroxyisovaleric acid, 2-hydroxy-2-methylbutanoic acid,α-hydroxy-n-caproic acid, α-hydroxyisocaproic acid,2-ethyl-2-hydroxybutanoic acid, 2-hydroxy-3,3-dimethylbutanoic acid,2-hydroxy-2-methylpentanoic acid, 2-hydroxy-5-methylhexanoic acid,2-hydroxy-2,4-dimethylpentanoic acid, 3-hydroxypropionic acid,β-hydroxybutyric acid, β-hydroxyisobutyric acid, β-hydroxy-n-valericacid, β-hydroxyisovaleric acid, 2-hydroxymethylbutanoic acid,hydroxypivalic acid, 3-hydroxy-2-methylpentanoic acid,1,1-hydroxytetradecanoic acid, jalapinolic acid, 1,4-hydroxyhexadecanoicacid, sabinic acid, juniperic acid, hydroxymalonic acid, methyltartronicacid, ethyltartronic acid, n-propyltartronic acid, isopropyltartronicacid, hydroxymethylmalonic acid, hydroxyisopropylmalonic acid,ethyl-hydroxymethyl-malonic acid, malic acid, α-methylmalic acid,α-hydroxy-α'-methylsuccinic acid, α-hydroxy-α', α'-dimethylsuccinic acidα-hydroxy-α', α'-diethylsuccinic acid, α-hydroxy-α'-ethylsuccinic acid,α-hydroxy-α'-methyl-α-ethylsuccinic acid, trimethylmalic acid,α-hydroxyglutaric acid, β-hydroxyglutaric acid,β-hydroxy-β-methylglutaric acid, α-hydroxyadipic acid, citric acid,isocitric acid, norcaperatic acid, agaricic acid, glyceric acid,α,β-dihydroxybutyric acid, α,β-dihydroxyisobutyric acid,β,β'-dihydroxyisobutyric acid, β,γ-dihydroxybutyric acid,α,γ-dihydroxy-β, β-dimethylbutyric acid, α,β-dihydroxy-α-isopropylbutyric acid, ipurolic acid, ustilic acid-A,9,10-dihydroxyoctadecanoic acid, tartaric acid (optically active orracemic body), mesotartaric acid, methyltartaric acid,α,β-dihydroxyglutaric acid, α,γ-dihydroxyglutaric acid,α,γ-dihydroxy-β-methylglutaric acid,α,γ-dihydroxy-β-methyl-β-ethylglutaric acid,α,γ-dihydroxy-α,γ-dimethylglutaric acid, α,δ-dihydroxyadipic acid,β-γ-dihydroxyadipic acid, 6,7 -dihydroxydodecanoic diacid, 7,8-dihydroxyhexadecanoic diacid, furoionic acid, trihydroxybutyric acid,trihydroxyisobutyric acid, trihydroxyglutaric acid, succinic acid,glutaric acid, adipic acid, α-methylglutaric acid, and dodecanoicdiacid.

Derivatives of the compounds represented by the above formula arelactones, acid anhydrides, alkali metal salts, alkaline earth metalsalts, salts with amines and the like. Examples thereof areβ-propiolactone, glycolide, lactide, β-methylpropiolactone,β,β-dimethylpropiolactone, β-n-propylpropiolactone,β-isopropylpropiotactone, β-methyl-β-ethylpropiolactone,γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone,ε-caprolactone, 1,5-hydroxypentadecanoic acid lactone,γ-butyrolactone-α-carboxylic acid, paraconic acid, α-methylparaconicacid, β-methylparaconic acid, α-ethylparaconic acid,α-isopropylparaconic acid, γ-methylparaconic acid, γ-ethylparaconicacid, α,γdimethylparaconic acid, β,γ-dimethylparaconic acid,α,α,β-trimethylparaconic acid, γ,γ-dimethylparaconic acid, nephrosteraicacid, γ-valerolactone-γ-carboxylic acid,γ-isopropyl-γ-butyrolactone-γ-carboxylic acid,α,α-dimethyl-γ-butyrolactone-γ-carboxylic acid,β-methyl-γ-valerolactone-γ-carboxylic acid,α,β-dimethyl-γ-valerolactone-γ-carboxylic acid,α,βdimethyl-γ-butyrolactone-γ-carboxylic acid, homoisocapric acid,α-(γ-hydroxycarbonylpropyl)-γ-butyrolactone, β-hydroxyadipicacid-γ-lactone, α,δ-dimethyl-β-hydroxyadipic acid-γ-lactone,β-hydroxy-β-methyladipic acid-γ-lactone,α-(δ'-carboxy-n-butyl)-γ-butyrolactone, α-methylisocitric acid lactone,cinchonic acid, α-hydroxy-γ-butyrolactone, β-hydroxy-γ-butyrolactone,δ-hydroxy-γ-valerolactone, pantolactone, mevalonic acid, malic acidanhydride, tartaric acid anhydride, hydroxyglutaric acid anhydride,α,β,γ-trihydroxyvaleric acid lactone,α-hydroxy-α-hydroxymethyl-γ-butyrolactone, succinic acid anhydride, andglutaric acid anhydride. These may be used singly or in combination oftwo or more.

Of these compounds especially preferred are tartaric acid, malic acid,citric acid and derivatives thereof. These include such acids incommercially available form (such as anhydrous state or hydrated state).Examples of useful derivatives are acetyl citrate, monostearyl citrate,and/or distearyl citrate, N,N'-diethylcitric acid amide,N,N'-dipropylcitric acid amide, N-phenylcitric acid amide,N-dodecylcitric acid amide, N,N'-didodecylcitric acid amide andN-dodecylcitric acid amide, calcium malate, calcium citrate, potassiummalate, and potassium citrate.

As other preferable polyfunctional compounds (E), mention may be made ofcompounds (H) which are characterized by having, in the molecule,simultaneously (a) an acid halide group, preferably an acid chloridegroup and (b) at least one of a carboxylic acid group, an acid anhydridegroup, a carboxylic acid ester group and an acid amide group, preferablya carboxylic acid group and a carboxylic acid anhydride group.

As examples of compounds (H), mention may be made of anhydrotrimelliticacid chloride, chloroformylsuccinic acid anhydride, chloroformylsuccinicacid, chloroformylglutaric acid anhydride, chloroformylglutaric acid,chloroacetylsuccinic acid anhydride, chloroacetylsuccinic acid,trimellitic acid chloride and chloroacetylglutaric acid.Anhydrotrimellitic acid chloride is especially suitable.

These compounds (F), (G) and (H) are mentioned in detail in U.S. Pat.Nos. 4,315,086 and 4,642,358. (These are incorporated by referenceherein.)

Other preferable polyfunctional compounds (E) are epoxy compounds (J)comprising a compound having an epoxy group in the molecule and/or acondensation polymer of dihydric phenol and epichlorohydrin.

Examples of epoxy compounds (J) are epoxides of olefins or cycloalkenessuch as ethylene oxide, propylene oxide and cyclohexene oxide.Furthermore, condensation products of dihydric phenol andepichlorohydrin at various ratios are included andtypical examplesthereof are condensates of bisphenol A and epichlohydrin (commerciallyavailable products are, for example, SUMIEPOXY® ELA-115, ELA-127,ELA-128, ELA-134, ESA-011, ESA-0,14, ESA-017, and ESA-019 of SumitomoChemical Co. Ltd. and phenol resins of Union Carbide Corp.), condensatesof resorcin and epichlorohydrin, condensates of hydroquinone andepichlorohydrin, condensates of tetrabromobisphenol A andepichlorohydrin, and glycidyl etherification products of phenol novolakor cresol novolak (e.g., a series of SUMIEPOXY® ESCN-220 of SumitomoChemical Co., Ltd.).

Furthermore, there are included[condensates of polyhydric alcohols andepichlorohydrin and typical examples of the polyhydric alcohols areethylene glycol, propylene glycol, butylene glycol, polyethylene glycol,polypropylene glycol, glycerine, trimethylolethane, trimethylolpropaneand pentaerythritol.

Further examples are glycidyl etherification products of monohydricphenols or monohydric alcohols such as phenylglycidyl ether,butylglycidyl ether and cresylglycidyl ether.

Further, mention may be made of glycidylation products of aminecompounds (commercially available are SUMIEPOXY® ELN-125 of SumitomoChemical Co. Ltd. which is a diglycidylation product of aniline).

Furthermore, there may be used polymers of epoxy-containing unsaturatedcompounds (such as glycidyl acrylate, glycidyl methacrylate, and allylglycidyl ether) and copolymers of epoxy-containing unsaturated compoundand at least one of other monomers (such as ethylene, propylene, butene,styrene, α-methylstyrene, 4-methyl-pentene, chlorostyrene, bromostyrene,acrylic acid, acrylic acid esters, acrylonitrile, vinyl chloride,methacrylic acid, methacrylic acid esters, maleic anhydride, and vinylacetate). Of these polymers especially preferred are styrene-glycidylacrylate or methacrylate copolymers and ethylene-glycidyl acrylate ormethacrylate copolymers and further preferred are ethylene-glycidylmethacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetatecopolymer and ethylene-glycidyl methacrylate-methyl acrylate copolymer.

As other preferable polyfunctional compounds (E), mention may be made oforganosilane compounds (K) which have in the molecule simultaneously (a)at least one silicon atom which bonds to a carbon atom through an oxygenatom, (b) carbon-carbon double bond or carbon-carbon triple bond, and(c) at least one functional group selected from an amino group, amercapto group, a carboxylic acid group, an acid anhydride group, anacid amide group, a carboxylic acid ester group, an imide group and ahydroxyl group.

In these compounds (K), a C-O-Si component is usually present as analkoxy group or an acetoxy group which directly bonds to a silicon atom.Such an alkoxy group or an acetoxy group generally has less than 15carbon atoms and may contain a heteroatom (e.g., oxygen). Further, inthese compounds, two or more silicon atoms may be present. When two ormore silicon atoms are present, these are bonded through an oxygen bond(e.g., in case of siloxane), a silicon-silicon bond, or a bifunctionalorganic group (e.g., a methylene group or a phenylene group).

Examples of suitable organosilane compounds (K) areγ-aminopropyltriethoxysilane, 2-(3-cyclohexenyl)ethyltrimethoxysilane,1,3-divinyltetraethoxysilane, vinyltris(2-methoxyethoxy)silane,5-bicycloheptenyltriethoxysilane and γ-mercaptopropyltrimethoxysilane.

As other preferable polyfunctional compounds (E), mention may be made ofolefin polymer compounds (P) having a carboxylic acid group in molecule.

As examples of polymer compounds (P), mention may be made ofethylene-acrylic acrid copolymer, ethylene-methacrylic acid copolymer,ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-methacrylicacid-ethyl acrylate copolymer, and alkali metal salts thereof(ionomers).

These olefin polymer compounds (P) can be produced, for example, bycopolymerizing an olefin and a compound having a carboxylic acid groupin main chain in the presence of a polymerization initiator and acatalyst. Generally, it is possible to produce them by knownhigh-pressure radical polymerization method mentioned below. They areobtained by copolymerization of ethylene and a radical copolymerizablemonomer (comonomer) using a free radical initiator such as organicperoxide or oxygen. The copolymerization reaction is carried outnormally at a polymerization temperature of 130°-300° C. and under apolymerization pressure of 500°-3,000 kg/cm².

The radical copolymerizable monomers include, for example, unsaturatedcarboxylic acids such as acrylic acid and methacrylic acid andesterification products thereof, and vinyl esters such as vinyl acetate.As the esterification products of unsaturated carboxylic acid, mentionmay be made of methyl acrylate, ethyl acrylate, and methyl methacrylate.These comonomers may be used singly or in combination of two or more.

Content of comonomer contained in olefin polymer compounds (P) is0.1-40% by weight, preferably 1-35% by weight. When content of comonomeris less than 0.1% by weight, modification effect cannot be obtained.

Among them, preferred are ethylene-acrylic acid copolymer andethylene-methacrylic acid copolymer.

Amounts of compounds (E) or (F), (G), (H), (J), (K) and (P) can bevariously selected depending on object, but is generally 200 parts byweight or less, preferably 80 parts by weight or less, more preferably20 parts by weight or less, and most preferably 0.01-10 parts by weightper 100 parts by weight of polyphenylene ether.

In modification of polyphenylene ether with the above-mentionedcompounds (E) or (F), (G), (H), (J), (K) and (P), radical initiators maybe used in some case. The radical initiators include known organicperoxides and diazo compounds. Preferred examples are benzoyl peroxide,dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide,tert-butyl hydroperoxide, cumene hydroperoxide, andazobisisobutyronitrile. Amount of the radical initiators is 0.01-10parts by weight, ]preferably 0.1-5 parts by weight per 100 parts byweight of polyphenylene ether.

With reference to the modified polyphenylene ether, it may be a chemicalreaction product of the above compound with polyphenylene ether or theabove compound and polyphenylene ether may be combined through physicalinteraction (e.g., physical adsorption to polyphenylene ether).

Furthermore, preferable modified polyphenylene ethers in the presentinvention include those which are obtained by graft polymerizing theunsaturated monomers (L) other than the above unsaturated polyfunctionalcompounds (E) or the polyfunctional compounds (E) and unsaturatedmonomers (L) other than potyfunctional compounds (E) on polyphenyleneether in the presence of radical initiators.

Such unsaturated monomers (L) include preferably vinyl and/or vinylidenecompounds (N) other than polyfunctional compounds (E). Examples of thecompounds (N) are shown below.

Aromatic vinyl or vinylidene compounds such as styrene, α-methylstyrene,o, m, and p-methylstyrenes, chlorostyrene, bromostyrene, divinylbenzene,hydroxystyrene, and aminostyrene; olefins such as ethylene, propylene,butene-1, pentene-1, hexene-1, -methylpentene-1, octene-1, decene-1, andoctadecene; cyanovinyl compounds such as acrylonitrile andmethacrylonitrile; vinyl ester compounds such as vinyl acetate; vinylether compounds such as methylvinyl ether, ethylvinyl ether, andbutylvinyl ether; and unsaturated halogen compounds such as vinylchloride and vinylidene chloride. These may be used singly or incombination of two or more. The most preferred unsaturated monomer to begraft copolymerized is styrene. The most preferred combinations ofcompounds (N) and compounds (E) are styrene-glycidyl methacrylate,styrene-glycidyl acrylate, styrenemaleic anhydride, styrene-acrylic acidand styrenemethacrylic acid.

Amount of unsaturated monomer (L) in the present invention is 200 partsby weight or less, preferably 0.5-100 parts by weight, more preferably1-50 parts by weight per 100 parts by weight of polyphenylene ether.

There is no limitation in process for production of modifiedpolyphenylene ether in the present invention and known processes can beused and examples are as follows.

(1) Polyphenylene ether and the above compound in the form of pellets,powders, or fine pieces are uniformly mixed by high-speed stirrers andmelt kneaded.

(2) The above compound is added to a solution prepared by dissolvingpolyphenylene ether in a solvent or swelling polyphenylene ether with asolvent to dissolve the compound therein or swell the compoundtherewith, followed by heating with stirring.

(3) The above compound is added to polyphenylene ether and the mixtureis dispersed in water, followed by heating with stirring.

In the case of (3), it is preferred to use dispersion stabilizers suchas polyvinyl alcohol, sodium dodecylbenzenesulfonate, and calciumphosphate. In some case, there may be added a solvent in whichpolyphenylene ether is dissolved or with which polyphenylene ether isswollen.

In the process of (1), temperature and time for melt kneading have nospecial limitation. Temperature somewhat varies depending on kinds andamount of the compounds, but is generally 150°-350° C. Apparatuses formelt kneading can be any of those used for methods which can handle amelt viscous material and either batch method or continuous method canbe employed. Examples are single-screw or multi-screw extruders, Banburymixer, roll, and kneader.

The solvent used in the process of (2) is not critical and may be onewhich can dissolve or swell polyphenylene ether.

As examples of the solvents, mention may be made of chloroform,methylene chloride, benzene, xylene, chlorobenzene, cyclohexane,styrene, toluene, and o-chlorophenol. Mixed solvents may be used as faras they can dissolve or swell polyphenylene ether. Temperature and timefor mixing are not critical and generally temperature is 20°-250° C. andtime is 1 minute--10 hours.

When modified polyphenylene ether is used in the present invention,preferably modified polyphenylene ether is previously prepared and thenthis is mixed with other components to obtain the thermoplastic resincomposition of the present invention. However, it is also possible toproduce the thermoplastic resin composition by simultaneously mixing theabove-mentioned compound as a modifier, polyphenylene ether and othercomponents.

In the present invention, a composition comprising polyphenylene etheror modified polyphenylene ether and aromatic vinyl polymer resin (M) mayalso be used as polyphenylene ether resin (B). The aromatic vinylpolymer resin (M) here means an aromatic vinyl polymer, a copolymer ofaromatic vinyl compound with other monomer, or a rubber modifiedaromatic vinyl polymer.

Aromatic vinyl polymer resins (M) are selected from those which have atleast 25% by weight of polymer unit derived from a monomer having thefollowing formula: ##STR9## [wherein R represents a hydrogen atom, alower alkyl group (such as an alkyl group of 1-4 carbon atoms) or ahalogen atom, Z represents a hydrogen atom, a vinyl group, a halogenatom, an amino group, a hydroxyl group or a lower alkyl group, and prepresents 0 or an integer of 1-5].

As examples of aromatic vinyl polymers and copolymers of aromatic vinylcompounds and other monomers, mention may be made of homopolymers suchas polystyrene, polychlorostyrene, and poly-α-methylstyrene andcopolymers thereof, and styrene-containing copolymers such asstyrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer,styrene-glycidyl methacrylate copolymer, styrene-acrylic acid copolymer,styrene-N-phenylmaleimide copolymer, styrene-divinylbenzene copolymer,and styrene-acrylonitrile-α-methylstyrene copolymer. Among them,preferred are polystyrene, styrene-α-methylstyrene copolymer,styrene-acrylonitrile copolymer, styrene-α-chlorostyrene copolymer,styrene-methyl methacrylate copolymer, styrene-glycidyl methacrylatecopolymer, styrene-maleic anhydride copolymer and styrene-acrylic acidcopolymer.

The rubber modified aromatic vinyl polymers are those which comprisearomatic vinyl polymer or copolymer matrix in which rubber particles aredispersed to form a two-phase system. They can be produced by mechanicalmixing of the rubber-like material (C) mentioned below and aromaticvinyl polymer or copolymer or by dissolving rubber-like material inaromatic vinyl compound monomer, followed by polymerizing the aromaticvinyl compound monomer therewith. According to the latter method,so-called high-impact strength polystyrenes are industrially produced.

The rubber-like material (C) used in the present invention is at leastone selected from natural and synthetic elastomeric polymers which areelastic at 20°-25° C. and modified elastomeric polymers obtained bymodifying the above elastomeric polymers with at least one compoundselected from polyfunctional compounds (E) and unsaturated monomers (L)in the presence or absence of a radical initiator.

Examples of the elastomeric polymers are natural rubber (NR), dienerubbers [such as polybutadiene (BR), polyisoprene (IR), andpolychloroprene (CR)]and copolymers of diene and vinyl monomer [such asstyrene-butadiene random copolymer (SBR), styrene-butadiene blockcopolymer (SB), styrene-butadiene-styrene block copolymer (SBS),styrene-isoprene random copolymer, styrene-isoprene block copolymer(SI), styrene-isoprene-styrene block copolymer (SIS), polybutadiene onwhich styrene is graft copolymerized, isoprene-acrylonitrile copolymer(NIR), butadiene-acrylonitrile copolymer (NBR)], or hydrogenatedproducts of these copolymers, polyiso-butylene (PIB), copolymers ofisobutylene and butadiene or isoprene (IIR), ethylene-α-olefincopolymer, ethylene-α-olefin-non-conjugated diene copolymer,ethylene-alkyl acrylate copolymers (such as ethylene-ethyl acrylatecopolymer and ethylenebutyl acrylate copolymer), polysulfide rubbers (T)such as thiokol rubber, acrylic rubbers (ACM,ANM), polyurethane rubber(U), polyether rubber, epichlorohydrin rubbers (CHR, CHC), polyesterelastomer and polyamide elastomer.

These elastomeric polymers can be produced by various processes such asemulsion polymerization, solution polymerization and bulkpolymerization, using various catalysts such as peroxides,trialkyl-aluminum, lithium halides and nickel-based catalysts.

Furthermore, there may also be used those which have variouscrosslinking degrees, various proportions of micro structures such ascis structure, trans structure and a vinyl group. In case of dienerubbers and copolymers of dienes and vinyl compounds, those which arevariously different in micro structure of double bond (vinyl group,cis-1,4 bond, trans 1,4-bond) are also used as elastomeric polymers ofthe present invention.

Further, random copolymers, block copolymers, and the like are used asthe elastomeric polymers of the present invention.

Moreover, these elastomeric polymers may also be produced bycopolymerization with other dienes.

Methods for the copolymerization may be any methods such as randomcopolymerization, block copolymerization and graft copolymerization.Examples of the monomers include butadiene, isoprene, andchlorobutadiene.

Preferred elastomeric polymers include copolymers comprising 40-100% byweight of butadiene and 60-0% by weight of styrene, copolymerscomprising 35-82% by weight of butadiene and 35-18 by weight ofacrylonitrile, styrene-butadiene and styrene-butadiene-styrene blockcopolymers (including all of linear block copolymers, radial blockcopolymers, etc.) and hydrogenated products thereof (SEB, SEBS),styrene-isoprene and styrene-isoprene-styrene block copolymers andhydrogenated products thereof (SEP, SEPS), styrene grafted polybutadiene(obtained by adding styrene to polybutadiene or butadienestyrenecopolymer latex and graft copolymerizing it with a radical initiator),ethylene-α-olefin copolymer and ethylene-α-olefin-non-conjugated dienecopolymer.

The ethylene-α-olefin copolymer rubbers include, for example, copolymersof ethylene with other α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene and terpolymerrubbers such as ethylene-propylene-1-butene copolymer, among whichethylene-propylene copolymer rubber (EPR) and ethylene-1-butenecopolymer rubber (EBR) are preferred.

Ethylene content in the ethylene-α-olefin copolymer rubber is 15-85% byweight, preferably 40-80% by weight. That is, crystalline copolymerswhich have an ethylene content of more than 85% by weight are difficultto be processed under normal rubber molding conditions and those whichhave an ethylene content of less than 15% by weight are high in glasstransition temperature (Tg) and lose elastic properties.

Number-average molecular weight of ethylene-α-olefin copolymer rubbersis such that they can be kneaded in extruders and is 10,000-100,000. Ifthe molecular weight is too low, handling at feeding to the extruders isdifficult and if it is too high, flowability is so small that processingis difficult.

Molecular weight distribution of ethylene-α-olefin copolymer rubbersalso has no special limitation and there may be used any copolymerrubbers having various molecular weight distribution such as monomodaltype and bimodal type which are usually commercially prepared and sold.

Value Q of molecular weight distribution (weight-average molecularweight/number-average molecular weight) is preferably 1-30, morepreferably 2-20.

Ethylene-α-olefin-non-conjugated diene copolymer rubber can also beused, but non-conjugated diene content in raw material rubber ispreferably 3% by weight or less. When non-conjugated diene content ismore than 3% by weight, there occurs gelation at kneading and this isnot preferred.

That is, the. copolymer rubbers .are those which are produced usingso-called Ziegler-Natta catalyst which is an ordinary productioncatalyst and, for example, combination of an organoaluminum compoundwith a tri˜pentavalent vanadium compound soluble in hydrocarbon solventsis used as the catalyst. As the aluminum compound, there may be usedalkylaluminum sesquichloride, trialkylaluminum, dialkylaluminummonochloride, or mixtures thereof and as the vanadium compound, theremay be used vanadium oxytrichloride, vanadium tetrachloride or vanadatecompounds represented by VO(OR⁸)_(q) X_(3-q) (0<q≦3, R⁸ is a straightchain or cyclic hydrocarbon of 1-10 carbon atoms).

Among styrene block copolymers, especially preferred are partiallyhydrogenated styrene-butadiene block copolymer or partially hydrogenatedstyrene-isoprene block copolymer which is a hydrogenated product. Theseare produced by hydrogenation treatment of styrene-butadiene blockcopolymer and styrene-isoprene block copolymer, respectively. Structureand process for production will be explained below.

As the partially hydrogenated styrene-butadiene block copolymer andpartially hydrogenated styrene-isoprene block copolymer (hereinafterreferred to as "hydrogenated block copolymer"), there may be usedhydrogenated block copolymers in which number-average molecular weightof block copolymer rubber is 10,000-1,000,000, preferably20,000-300,000, number-average molecular weight of aromatic vinylpolymer block A in block copolymer rubber is 1,000-200,000, preferably2,000-100,000, number-average molecular weight of conjugated dienepolymer block B is 1,000-200,000, preferably 2,000-100,000 and weightratio of aromatic vinyl polymer block A and conjugated diene polymer Bis 2/98-60/40, preferably 10/90-40/60.

For production of block copolymer rubbers, many processes have beenproposed and according to a representative process which is disclosed inJapanese Patent Kokoku No. 40-23798, a block copolymer rubber ofaromatic vinyl hydrocarbon and diene hydrocarbon can be obtained byblock copolymerization in an inert solvent using a lithium catalyst or aZiegler type catalyst.

A hydrogenation treatment of these block copolymer rubbers is carriedout in an inert solvent in the presence of a hydrogenation catalyst bythe processes disclosed, for example, in Japanese Patent Kokoku Nos.42-8704, 43-6636 and 46.-20814. Hydrogenation rate is at least 50%,preferably at least 80% of polymer block B and 25% or .less of aromaticunsaturated bond in polymer block A is nuclear-hydrogenated.Representative examples of such partially or completely hydrogenatedblock copolymers are thoses which are sold in the tradename of KRATON®-Gby Shell Chemical Co., U.S.A.

The modified elastomeric polymers in the present invention are thosewhich are obtained by modifying elasnomeric polymers with at least onemodifier selected from polyfunctional compounds (E) having at least oneof a carboxylic acid group, an acid anhydride group, an acid amidegroup, an imide group, a carboxylic acid ester group, an epoxy group, anamino group, and a hydroxyl group in molecule and unsaturated monomers(L) other than the polyfunctional compounds (E) in the presence orabsence of a radical initiator. These modifiers and amount of modifiershave already mentioned in the part of explanation on process forproduction of modified polyphenylene ether.

For production of modified elastomeric polymer, known processes may beused and specifically those which have been mentioned in the part onproduction of modified polyphenylene ether may be employed.

In the present invention, as one of preferred embodiments for productionof modified ethylene-α-olefin copolymer rubber-modified hydrogenatedblock copolymer, it can be obtained by graft copolymerization usingunsaturated carboxylic acid or derivative thereof as modifiers(hereinafter referred to as "graft monomer"), preferably in combinationwith aromatic vinyl monomer for respective: starting materials and, ifnecessary, in the presence of a radical initiator. Process forproduction. of the modified elastomeric polymers will be specificallyexplained below.

Various known processes can be employed for graft copolymerization ofgraftable monomer on the starting elastomeric polymers in production ofthe modified elastomeric polymers.

For example, there are a process which comprises mixing a startingelastomeric polymer, a graftable monomer and a radical initiator andmelt kneading the mixture in a melt kneading apparatus to performgrafting, a process which comprises dissolving a starting elastomericpolymer in an organic solvent such as xylene, then adding a radicalinitiator in nitrogen atmosphere, heating the mixture to allow areaction to proceed under stirring, followed by cooling, washing,filtering and drying to obtain grafted elastomeric polymer, a processwhich comprises irradiating a starting elastomeric polymer withultraviolet ray or radiation in the presence of a graftable monomer, anda process of contacting with oxygen or ozone.

The process of carrying out graft copolymerization by melt kneading inmelt kneading apparatuses is most preferred from an economicalviewpoint.

The modified elastomeric polymers can be obtained by melt kneadingstarting elastomeric polymers, unsaturated carboxylic acids orderivatives thereof and, if necessary, in the presence of radicalinitiators or starting elastomeric polymers, unsaturated carboxylicacids or derivatives thereof, preferably in combination with aromaticvinyl monomers and, if necessary, in the presence of radical initiatorsa temperature of 200°-280° C., preferably 230°-260° C. and for aresidence time of 0.2-10 minutes which varies depending on kind ofradical initiators by an extruder, Banbury mixer, a kneader and thelike.

When kneading is carried out in the presence of too much oxygen,gel-like materials may be produced or considerable coloration may occurand so kneading is preferably carried out in the presence ofsubstantially no oxygen.

Furthermore, when kneading temperature is lower than 200° C., desiredaddition amount of unsaturated carboxylic acids or derivatives thereofis not obtained and besides, only a small effect can be obtained onimprovement of graft reaction amount. Even if the temperature exceeds280° C., effect of improvement of reaction amount is small and in somecase, there may cause production of gel-like materials or coloration.

Kneading machines used for modification have no special limitation, butit is generally preferred to use extruders because continuous productionis possible. The extruders preferably have screws suitable for uniformmixing of various starting materials supplied through single ortwin-screws. In order to remove from reaction product unalteredcomponents (unsaturated carboxylic acids or derivatives thereof,aromatic vinyl monomers, radical initiators) and side-reaction productssuch as oligomers and decomposition products of the unalteredcomponents, there may be carried out suction by vacuum pumps from ventlines in the midway or in the vicinity of exits of the extruders orpurification by dissolving the reaction product in a suitable solventand then precipitating it. It is also possible to conduct the heattreatment at higher than 60° C. or drawing under vacuum and melting.

The above three components or four components can be respectivelyseparately fed to kneading machines or a part or all of them can bepreviously uniformly mixed and then fed to the kneading machines. Forexample, elastomeric polymers are impregnated with radical initiatorsand aromatic vinyl monomers and are fed simultaneously with unsaturatedcarboxylic acid or derivatives thereof at the time of kneading and thenthese are kneaded. Furthermore, modification can also be carried out byfeeding radical initiators, unsaturated carboxylic acids or derivativesthereof, or aromatic vinyl monomers from the points in the midway ofextruders.

If necessary, various additives such as antioxidants, heat stabilizers,light stabilizers, nucleating agents, lubricants, antistatic agents,inorganic or organic colorants, rust preventers, crosslinking agents,foaming agents, plasticizers, fluorescent agents, surface smoothingagents, and surface gloss improvers can be added to the modifiedelastomeric polymer at the preparation step or subsequent processingstep.

Unsaturated carboxylic acids or derivatives thereof and radicalinitiators used for modified elastomeric polymer can be selected fromcompounds used for production of graft polypropylene. As aromatic vinylmonomers, styrene is most preferred, but o-methylstyrene,p-methylstyrene, α-methylstyrene, vinyltoluene, and divinylbenzene mayalso be used. These may also be used in admixture.

In production of modified elastomeric polymers, aromatic vinyl monomersare used for inhibition of gel formation and improvement of graftreaction amount. Amount of aromatic vinyl monomers used per 100 parts byweight of the starting elastomaric polymers is preferably 0.2-20 partsby weight and amount of unsaturated carboxylic acids or derivativesthereof are preferably 0.5-15 parts by weight. When aromatic vinylmonomers are used, amount of unsaturated carboxylic acids or derivativesthereof used are preferably 0.5-15 parts by weight and weight ratio ofaromatic vinyl monomers/unsaturated carboxylic acids or derivativesthereof is preferably 0.1-3.0, more preferably 0.5-2.0.

When the weight ratio of aromatic vinyl monomers to unsaturatedcarboxylic acids or derivatives thereof is lower than 0.1, effects ofinhibition of gel formation and an improvement in graft reaction amountare not seen and even when it is used at the weight ratio higher than3.0, no further preferable effect can be expected.

Amount of radical initiators varies depending on kind of radicalinitiators and kneading conditions, but is usually 0.005-1.0 part byweight, preferably 0.01-0.5 part by weight per 100 parts by weight ofthe starting elastomeric polymers. When it is less than 0.005 part byweight, desired addition amount of unsaturated carboxylic acids orderivatives thereof cannot be obtained and effect of increasing ofaddition amount of unsaturated carboxylic acids or derivatives thereofdue to use of aromatic vinyl monomers used in combination is small. Whenit is more than 1.0 part by weight, gel-like materials are produced andthis is not preferred.

The thus obtained modified elastomeric polymers have addition amount ofunsaturated carboxylic acids or its derivatives of 0.1-5% by weight andpreferably has an addition amount of aromatic vinyl monomers of 0.1-5%by weight and preferably has a Mooney viscosity (ML₁₊₄, 121° C.) of5-120.

Dinitrodiamines (D) which play the most important part for improvingcompatibility between the polyolefin resin (A) and the polyphenyleneether resin (B) in the composition of the present invention are thosewhich are represented by the formula (I): ##STR10## (wherein X is adivalent chain aliphatic group, a cyclic aliphatic group or an aromaticgroup which may contain a halogen or oxygen atom; R¹ is a hydrogen atom,a chain aliphatic group, a cyclic aliphatic group, or an aromatic group,and when both X and R¹ are chain aliphatic groups, the nitrogen atomsmay further bond each other to form a ring through X and R¹ ; and R² andR³ are independently a hydrogen atom or an alkyl group or 1-12 carbonatoms, and R² and R³ may bond to form a ring).

Dinitrodiamines represented by the formula (I) can be easily produced bycondensation reaction of diamines, nitroalkanes and formaldehyde asstarting materials in inert solvents such as methanol. A small amount ofan alkaline compound may be used as a catalyst for acceleration ofreaction in production.

The following compounds can be exemplified as compounds comprising suchdinitrodiamines. In the examples, --Z represents ##STR11##

As shown above, substituent X in the formula (I) is a divalent chainaliphatic group, cyclic aliphatic group or aromatic group and cancontain halogen as in the above examples (33) and (34) and moreover, cancontain oxygen as in examples (40)-(43). Among them, suitable are chainaliphatic groups, especially those of 4-12 carbon atoms.

R¹ in the formula (I) is a hydrogen atom, a chain aliphatic group, acyclic aliphatic group or an aromatic group and when X and R¹ are bothchain aliphatic groups, there are included such cases where nitrogenatoms further bond each other to form a ring through X and R¹, and X, R¹and two nitrogen atoms bond together to form a ring as shown in theabove examples (23) and (24).

R² and R³ in the formula (I) may be identical or different and areindependently a hydrogen atom or an alkyl group of 1-12 carbon atoms. R²and R³ may bond to each other to form a ring as in the above examples(12), (13), (22) and (30).

Compounds (D) comprising the dinitrodiamines as shown above may besingle compound or mixture of two or more compounds or mixture withfillers such as silica and talc or with other ad. ditives. Therefore,they. may be used in any of these forms.

The thermoplastic resin composition of (A)/(B)/(D) or (A)/(B)/(C)/(D) ofthe present invention is excellent in mechanical properties and solventresistance. In some case, flowability is further required depending onmolding methods. Especially, in the case of injection molding, a highflowability is required. In order to improve flowability, it ispreferred to further add polyolefin and/or elastomeric polymers to thecompositions of (A)/(B)/(D) or (A)/(B)/(C)/(D). These compositions arealso thermoplastic resin compositions of the present invention.

In practice of the present invention, other polymer compounds or aidscan also be added to the thermoplastic resin compositions of the presentinvention. Other polymer compounds include, for example, polymers suchas polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate,polyvinylpyridine, polyvinylcarbazole, polyacrylamide, andpolyacrylonitrile, polycarbonate, polysulfone, polyether sulfone,polyethylene terephthalate, polybutylene terephthalate, polyaryleneester (such as U polymer of Unitika, Ltd.), polyphenylene sulfide,polyamides such as 6-nylon, 6,6-nylon, and 12-nylon; condensationpolymer compounds such as polyacetal; and various thermosetting resinssuch as silicone resin, fluororesin, polyimide, polyamideimide, phenolicresin, alkyd resin, unsaturated polyester resin and Dapon resin.

Polyesters or polyamides are preferred among the above polymercompounds.

In the present invention, fillers may be used for reinforcement,imparting function or extending (cost-cutting) to obtain thermoplasticresin compositions.

As fillers, there may be used fibers such as glass fibers, carbonfibers, polyamide fibers, metallic fibers, e.g., aluminum and stainlesssteel, and metal whisker, and inorganic fillers such as silica, alumina,calcium carbonate, talc, mica, clay, kaolin, magnesium sulfate,wallastonite, carbon black, TiO₂, ZnO, and Sb₂ O₃.

All of these fillers can be used. for reinforcement. Fillers such ascarbon fibers, metallic fibers, and carbon black can reduce surfaceresistivity and volume resistivity and can impart electricalconductivity to the thermoplastic resin compositions of the presentinvention. Fillers cheaper than resins can be used as extenders toattain cost-cutting.

When stiffness and heat resistance of the thermoplastic resincompositions of the present invention are to be improved, it isespecially preferred to use inorganic fillers such as glass fibers,potassium titanate whisker, talc, mica, and calcium carbonate or carbonfibers.

It is one of the preferred embodiments to use the thermoplastic resincompositions as a composite which additionally contains flame retardantsor flame retardant aids such as Sb₂ O₃, halides, and phosphate esters,lubricants, nucleating agents, plasticizers such as triphenyl phosphateand phthalate esters, dyes, pigments, antistatic agents, antioxidants,and weathering resistance imparting agents.

In the composition (R-1) comprising the polyolefin-resin (A) and thepolyphenylene-etherresin (B) in the present invention, thepolyolefinresin (A) is contained in an amount of 95-5% by weight,preferably 90-20% by weight and the polyphenylene-ether-resin (B) is inan amount of 5-95% by weight, preferably 10-80% by weight. When thepolyolefin-resin (A) is in an amount of less than 5% by weight,processability, toughness, water resistance, organic solvent resistance,and chemical resistance are not sufficient and when it is in an amountof more than 95% by weight, heat resistance and stiffness are notsufficient.

In the composition (R-2) comprising the polyolefin-resin (A), thepolyphenylene-ether-resin (B) and the rubber-like materials (C) in thepresent invention, the polyolefin-resin (A) is contained in an amount of94-2% by weight, preferably 90-20% by weight and thepolyphenylene-ether-resin (B) is contained in an amount of 2-94% byweight, preferably 10-80% by weight. When amount of the polyolefin-resin(A) is less than 2% by weight, processability, toughness, waterresistance, organic solvent resistance, and chemical resistance are not10 sufficient and when it is more than 94% by weight, heat resistanceand stiffness are not sufficient. Furthermore, the rubber-like material(C) used for an improvement in impact resistance is added in an amountof 1-50% by weight, preferably 3-35% by weight, more preferably 5-25% byweight. When amount of the rubber-like material (C) is less than 1% byweight, this is insufficient for improving impact resistance and when itis more than 50% by weight, deterioration in heat resistance andstiffness is conspicuous and desired results cannot be obtained.

Dinitrodiamines (D) are added in an amount of 0.001-10 parts by weight,preferably 0.01-8 parts by weight, more preferably 0.1-5 parts by weightper 100 parts by weight of the composition (R-1) or (R-2). When amountof the dinitrodiamine is less than 0.001 part by weight, effect toimprove compatibility is small and when it is more than 10 parts byweight, the effect reaches saturation and it remains as unaltered matterin the polymer and emits offensive odor and besides deterioration ofproperties is brought about and thus good results are not obtained.

To 100 parts by weight of the thermoplastic resin composition comprisingthe composition (R-1) or the (R-2) and a dinitrodiamine (D) are added1-1800 parts by weight of the polyolefin and/or 1-100 parts by weight ofthe elastomeric polymers, whereby a thermoplastic resin compositionexcellent in flowability and properties can be obtained. Amount of thepolyolefin must be less than 95% by weight based on the total amount ofthis polyolefin and the polyolefin-resin (A) contained in thecomposition (R-1) or (R-2). When this is 95% by weight or more,compatibility with the polyphenylene-ether-resin (B) reduces to causedeterioration of properties.

When the elastomeric polymers are added to 100 parts by weight ofthermoplastic resin compositions comprising the composition (R-1) andthe dinitrodiamines (D) and when the amount thereof is less than 1 partby weight, an improvement in impact resistance is insufficient and whenit is more than 100 parts by weight, deterioration of heat resistanceand stiffness is conspicuous and good results are not obtained. When theelastomeric polymers is added to the thermoplastic resin compositioncomprising the composition (R-2) and the dinitrodiamines (D), amount ofthe elastomeric polymers is less than 95% by weight based on the totalamount of the rubberlike materials (C) in the composition (R-2) and theelastomeric polymers added. Use of the elastomeric polymers and therubber-like materials (C) in combination gives good result inflowability, but when amount of the elastomeric polymers is 95% byweight or more, compatibility with the polyphenylene-ether-resin (B)lowers and properties are deteriorated.

Method for producing the thermoplastic resin compositions of the presentinvention has no special limitation and ordinary known methods can beemployed.

A method in which the components are mixed in the form of solution andthe solvent is evaporated or in which the components are precipitated ina non-solvent, is effective. However, from an industrial viewpoint, amethod of kneading them in molten state is employed in practice. Meltkneading is carried out using a kneading machine as generally-usedsingle-screw or twin-screw extruders, Banbury mixer, roll, and variouskneaders. A twin-screw extruder is especially preferred.

In kneading, it is preferred to previously uniformly mix respectiveresin components in the form of powder or pellet using such a device asa tumbler or a Henschel mixer. However, if necessary, each resincomponent may be separately fed directly to a kneading apparatus in afixed amount without the mixing.

Preferable method for producing the thermoplastic resin compositions ofthe present invention is mentioned below. First, the composition (R-1)(polyolefin-resin (A)/polyphenylene-ether-resin (B)) or the composition(R-2) ((A)/(B)/rubberlike materials (C)), a modifier and a radicalinitiator are melt kneaded using a high-kneading twin-screw extruder toprepare the composition (R-3) or (R-4) and then, dinitrodiamines (D)and, if necessary, polyolefin and/or elastomeic polymers are added tothe resulting composition (R-3) or (R-4), followed by melt kneading toobtain the thermoplastic resin compositions.

The compositions (R-3) and (R-4) can be produced specifically by thefollowing process.

The composition (R-3) can be produced by adding to 100 parts by weightof the composition (R-1) 0.01-20 parts by weight of polyfunctionalcompounds (E) containing 0.01-20 parts by weight of unsaturated monomers(L) or not, and 0.001-10 parts by weight of radical initiators and meltkneading them.

The composition (R-4) can be produced by adding to 100 parts by weightof the composition (R-2) 0.01-20 parts by weight of the polyfunctionalcompound (E) containing 0.01-20 parts by weight of unsaturated monomer(L) or not, and 0.001-10 parts by weight of radical initiators and meltkneading them.

Amount of the polyfunctional compound (E) used in production of thecomposition (R-3) or (R-4) is preferably 0.05-10 parts by weight, morepreferably 0.1-5 parts by weight and when the unsaturated monomers (L)are used, amount thereof is preferably 0.05-10 parts by weight, morepreferably 0.1-5 parts by weight. Amount of the radical initiators is0.001-10 parts by weight, preferably 0.005-5 parts by weight, morepreferably 0.1-2 parts by weight.

When amount of the polyfunctional compound (E) is less than 0.01 part byweight, effect of modification of the composition (R-1) or (R-2) issmall and when it is more than 20 parts by weight, modification effectreaches saturation and conspicuous effect is not exhibited and besides,it remains as unaltered material in the polymer and emits offensive odorand further deteriorates properties. Thus, good results cannot beobtained.

When an addition amount of the radical initiators is less than 0.001part by weight, effect on grafting reaction of the polyfunctionalcompounds (E) and the unsaturated monomers (L) is small and when it ismore than 10 parts by weight, further conspicuous effect on graftingreaction of the polyfunctional compounds (E) and the unsaturatedmonomers (L) is not exhibited and decomposition or crosslinking ofpolyolefins occurs much and change in flowability (melt flow rate) isgreat and such are practically not preferred.

Addition amount of the dinitrodiamines (D) is 0.001-10 parts by weight,preferably 0.01-8 parts by weight, more preferably 0.1-5 parts by weightper 100 parts by weight of the composition (R-3) or (R-4). When theamount is less than 0.001 part by weight, effect to improvecompatibility is small and when it is more than 10 parts by weight, theeffect reaches saturation and the dinitrodiamines remain as unsaturatedmaterials in the polymer and emit offensive odor and besides, bringabout deterioration of properties. Thus, good results cannot beobtained.

In order to more effectively produce thermoplastic resin compositions inthe present invention, it is preferred to use a high kneading twin-screwextruder having a long L/D and is provided with two or more feedopenings. Specifically, there are (1) a method of production by feedingthe polyolefin-resin (A) and the polyphenylene-ether-resin (B) and, ifnecessary, the rubber-like materials (C), the modifiers and the radicalinitiators in fixed amounts from the first feed opening and thedinitrodiamines (D) and, if necessary, polyolefin and/or elastomericpolymers in fixed amounts from the second feed opening and melt kneadingthem or (2) a method of production by feeding thepolyphenylene-ether-resin (B) and, if necessary, the rubber-likematerials (C) in fixed amounts from the first feed opening and thepolyolefin-resin (A) and, if necessary, the modifiers and the radicalinitiators in fixed amounts from the second feed opening, and thedinitrodiamines (D) and, if necessary, polyolefin and/or elastomericpolymers in fixed amounts from the third feed opening and melt kneadingthem.

The thermoplastic resin composition of the present invention can beeasily molded into molded products by general molding methods such asinjection molding, compression molding, blow molding, roll molding,laminate molding, vacuum molding, and air-pressure molding. The presentinvention further includes a method in which molded articles areobtained by dry-blending the components at the time of injection moldingor extrusion molding and then directly kneading the components duringmelt processing operation, without the previous kneading.

Among these molding methods, injection molding is desired from the pointof productivity. Pellets of the composition are previously dried byvacuum dryers or hot-air dryers and injection molded under givenconditions such as injection speed, injection time, and coolingtemperature to obtain molded products.

The molded products obtained from the thermoplastic resin compositionsof the present invention can be applied to automobile parts andelectrical and electronic parts. As.examples of automobile parts,mention may be made of exterior parts such as bumper, fender, apron,hood panel, fascia, rocker panel, rocker panel reinforce, floor panel,rear quarter panel, door panel, door support, roof top, and trunk lid,interior parts such as instrument panel, console box, glove box, shiftknob, pillar garnish, door trim, handle, arm rest, wind louver, carpet,heat rest, seat belt, and seat, parts of engine room such as distributorcap, air cleaner, radiator tank, battery case, radiator shroud, washertank, cooling fan, and heater case, mirror body, wheel cover, trunktrim, trunk mat, and gasoline tank.

Among these automobile parts molding products, the thermoplastic resincomposition of the present invention is suitably used for bumper andfender which require excellent stiffness and surface impact strength atlow temperature.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 shows an example of measured chart in evaluation of penetrationimpact strength in Example 1. Abscissa axis shows displacement amount(D:mm) which indicates deformation of test pieces and ordinate axisshows stress (N:Newton) corresponding to a certain displacement amount.

Yield point is the point at which stress corresponding to displacementamount changes from increase to decrease and breaking point is the pointat which a material is broken and no longer shows change of stress.

Yield point energy is areal integral of displacement amount and stressfrom rising portion of detected stress to yield point of materials andtotal energy is areal integral of displacement amount and stress fromrising portion to break point of materials.

EXAMPLES

The present invention will be explained by the following examples, itbeing understood that these examples are not intended to limit thepresent invention to them as far as they do not depart from the gist ofthe present invention.

Methods for measurement of properties in these examples are shown below.

(1) Melt flow rate:

This is measured according to JIS K6758. Measuring temperature is 260°C. andload is 2.16 unless otherwise notified.

(2) Tensile test:

This is measured according to ASTM D638. Thickness of test piece is 3.2mm and tensile yield strength and tensile elongation are evaluated.Measuring temperature is 23° C. unless otherwise notified.

(3) Flexural test:

This is measured according to JIS K7203. Flexural modulus and flexuralstrength are evaluated under the conditions of thickness of test pieces:3.2 mm, span length: 50 mm, and loading rate: 1.5 mm/min. Measuringtemperature is 23° C. unless otherwise notified. In case of employingother temperatures, measurement is conducted after conditioning for 30minutes in a constant-temperature bath of a given temperature.

(4) Izod impact strength:

This is measured according to JIS K7110. Thickness of test pieces is 3.2mm and notched impact strength is evaluated. Measuring temperature is23° C. unless otherwise notified. In case of employing othertemperatures, measurement is conducted after conditioning for 2 hours ina constant-temperature bath of a given temperature.

(5) Penetration impact strength:

High Rate Impact Tester (RIT-8000) manufactured by Rheometrics Co.(U.S.A.) is used. A plate test piece of 3 mm thick is fixed by acircular holding fixture of 2 inches and an impact probe of 5/8 inch(point spherical surface 5/16 inch R) is struck on the test piece at arate of 3 m/sec and displacement amount and stress are detected. Basedthereon a curve as shown in FIG. 1 is drawn and areal integral value iscalculated, whereby penetration impact strength is evaluated.

FIG. 1 is an example of measurement chart in evaluation of penetrationimpact strength in Example 2. Abscissa axis shows displacement amountwhich indicates deformation of test pieces and ordinate axis showsstress (N:Newton) corresponding to displacement amount. Both the valuesare continuously detected and are continuousfLy plotted in an X-Yplotter to obtain the measurement chart.

Areal integration of displacement amount and stress from rising portionof detected stress to yield point of materials is conducted. to obtainyield point energy and areal integration of displacement amount andstress from the rising portion to break point of the materials isconducted to obtain total energy.

For breaking state, whether it is ductile fracture (D) or brittlefracture (B) is judged by observing actual test pieces subjected to thedestructive test.

Energy value required for yielding of materials is evaluated by yieldpoint energy and energy value required for breaking of the materials isevaluated by total energy and are both expressed by joule (J) .

Conditioning is carried out by a constant-temperature bath attached tothe apparatus. A test piece is put in a constant-temperature bathpreviously adjusted to a given temperature and conditioning is carriedout for 2 hours and then the above test is conducted. This temperatureis measuring temperature.

(6) Heat distortion temperature:

This is measured by JIS K7207. Fiber stress is measured at 4.6 kg/cm .

(7) Mooney viscosity:

This is measured according to JIS K6300. Measuring temperature is 121°C.

(8) Ethylene content:

A pressed sheet is made from the composition and ethylene content isobtained by a calibration method using absorbance of characteristicabsorption of methyl (--CH₃) and methylene (--CH₂ --) which appear ininfrared absorption spectrum measured on the pressed sheet.

(9) Intrinsic viscosity:

Reduced viscosities are measured at three points of concentrations of0.1, 0.2, and 0.5 g/dl using Ubbelohde's viscometer. Intrinsic viscosityis obtained by the calculation method mentioned in "Polymer Solution,Polymer Experimental Study 11", (published from Kyoritsu Shuppan Co.,1982), page 491, namely, an extrapolation method which comprisesplotting reduced viscosities for concent.ration and extrapolatingconcentration at 0.

Test pieces used for the above evaluation of properties were producedunder the following injection molding conditions unless otherwisenotified. Composition was dried at 120° C. for 2 hours by a hot-airdryer and then was injection molded at a molding temperature of 260° C.and a mold cooling temperature of 50° C. for an injection time of 15seconds and a cooling time of 30 seconds by IS150 E-V type injectionmolding machine manufactured by Toshiba Machine Co., Ltd.

The following compositions were prepared under the following conditionsunless otherwise notified. Respective components were weighed in givenamounts, preliminarily uniformly mixed by a Henschel mixer and thenmolded by a continuous twin-screw kneading machine (TEX 44 SS 30BW-2Vmanufactured by Nippon Seikosho K. K.) at an extrusion amount of 30kg/hour, a resin temperature of 260° C., and at a screw rotation rate of350 rotations/min under suction from a vent. Regarding screws, rotors oftriple thread type and kneading discs of triple thread type werearranged in two places respectively next to the first feed opening andthe second feed opening in the kneading zone.

Reference Example 1 [Polyolefin-resin (A)]

Polypropylene was prepared by the slurry polymerization method mentionedin Japanese Patent Kokai No. 60-28405. Melt flow rate of polypropylenewas measured at 230° C. under a load of 2.16 kg. The same applies to thefollowing.

<PP-1>

Crystalline propylene homopolymer having a melt flow rate of 0.5 (g/10min) and an intrinsic viscosity of 3.05 (dl/g) measured in tetralinsolvent at 135° C. wherein content of a fraction soluble in cold xyleneof 20° C. is 2.9% by weight, content of a boiling heptane solublefraction is 6.7% by weight and isotactic pentad of a boilingheptaneinsoluble fraction is 0.952.

<PP-2>

Crystalline propylene/ethylene block copolymer having a melt flow rateof 7.5. (g/10 min) and an intrinsic viscosity of 2.18 (dl/g) measured intetralin at 135° C. wherein proportion of a propylene homopolymerportion (hereinafter referred to as "portion P") which is the firstsegment polymerized at the first step is 84% by weight, proportion of anethylene-propylene copolymer portion (hereinafter referred to as"portion EP") which is the second segment polymerized at the second stepis 16% by weight, molecular structure of the portion P is such thatintrinsic viscosity in tetralin solvent at 135° C. is 1.35 (dl/g),content of a fraction soluble in cold xylene of 20° C. is 2.6% byweight, content of a boiling heptane-soluble fraction is 7.0% by weightand isotactic pentad of a boiling heptane-insoluble fraction is 0.957and molecular structure of the portion EP is such that intrinsicviscosity in tetralin at 135° C. is 4.8 (dl/g), and ratio ofethylene/propylene in a portion EP is 37/63 by weight.

<PP-3>

Highly crystalline polypropylene having an intrinsic viscosity of 2.42(dl/g) in tetralin solvent at 135° C. and a melt flow rate of 1.6 (g/10min) wherein content of a fraction soluble in cold xylene of 20° C. is0.6% by weight, content of a boiling heptane soluble fraction is 2.9% byweight, and isotactic pentad of a boiling heptane-insoluble fraction is0.980.

<PP-4>

Crystalline propylene homopolymer having an intrinsic viscosity of 1.30(dl/g) in tetralin solvent at 135° C. and a melt flow rate of 36 (g/10min) wherein content of a fraction soluble in cold xylene of 20° C. is3.2% by weight, content of a boiling heptane-soluble fraction is 7.0% byweight, and isotactic pentad of a boiling heptane-insoluble fraction is0.952.

<PP-5>

Crystalline propylene homopolymer having a melt flow rate of 1.3 (g/20min) and an intrinsic viscosity of 2.45 (dl/g) in tetralin at 135° C.wherein content of a fraction soluble in cold xylene of 20° C. is 2.9%by weight, content of a boiling heptane-soluble fraction is 6.7% byweight, and isotactic pentad of a boiling heptane-insoluble fraction is0.955.

Modified polypropylene was prepared by the following process.

<M-PP-1>

100 parts by weight of PP-5 and 1.0 part by weight of maleic anhydride,0.6 part by weight of propylene homopolymer on which 8% by weight of1,3-bis(t-butylperoxyisopropyl)benzene (SANPEROX® -TY1.3 manufactured bySanken Kako Co.) was supported as a radical initiator, and 0.1 part byweight of a stabilizer IRGANOX® 1010 (manufactured by Ciba Geigy Co.)were uniformly mixed by a Henschel mixer and then melt kneaded by atwin-screw extruder TEX 44SS-30BW-2V manufactured by Nippon Seikosho K.K. at 220° C. and average residence time of 1.5 minute to produce maleicanhydride-modified polypropylene having addition amount of maleicanhydride of 0.08 by weight and a melt flow rate of 36 (g/10 min).Reference Example 2 [Polyphenylene-ether-resin (B)]

<PPE-1>

Poly-2,6-dimethylphenylene ether having an intrinsic viscosity of 0.30(dl/g) measured in chloroform of 25° C. was used as polyphenylene-ether.Reference Example 3 [Rubber-like material (C)]

<EPR-1>

Ethylene-propylene copolymer rubber (ESPRENE® E 111P) having a Mooneyviscosity at 121° C. of 33 and having an ethylene content of 73% byweight was used as a rubber-like material.

<SEP-1>

Partially hydrogenated styrene-isoprene block copolymer (KRATON® G1701manufactured by Shell Chemical Co.) was used as styrene copolymerrubber.

Reference Example 4 [Dinitrodiamines (D)]

<DNA-1>

In a 1 liter four-necked flask equipped with a stirrer, a thermometer,and a condenser were charged 116.2 g (1.0 mol) of 1,6-diaminohexane,178.2 g (2.0 mol) of 2-nitropropane, and 140 g of methanol and then,thereto was added dropwise 162.3 g (2.0 mol) of 37% formalin over aperiod of 1 hour at 45-55° C. with stirring. After addition of formalin,the content was kept at the same temperature for 1 hour and thenseparated into layers with addition of 200 ml of water.

The oil layer was washed with 200 ml of water and then concentratedunder the conditions of 60° C. and 30 Torr to obtain 304 g of lightyellow liquid. This liquid was analyzed by high performance liquidchromatography to find that it contained 298 g ofN,N'-bis(2-methyl-2-nitropropyl)-l,6diaminohexane and 5 g of2-nitropropane.

To this liquid were added 300 ml of n-hexane and 150 ml of toluene tocarry out dissolution, followed by cooling to 5° C. to result in aslurry with precipitation of crystal. This mixture was filtered and theresulting crystal was washed with 100 ml of cold n-hexane and thereafterwas vacuum dried at lower than 20° C. to obtain 288 g of N,N'-bis(2-methyl-2-nitropropyl) -1,6-diaminohexane.

This compound was light yellow crystal and had a melting point of26°-27° C.

Elemental analysis values of this compound were as follows.

    ______________________________________                                               C           H       N                                                  ______________________________________                                        Found    52.69%        9.45%   17.57%                                         Calcd.   52.81%        9.50%   17.60%                                         ______________________________________                                    

Reference Example 5 [Masterbatch of dinitrodiamines (D)]

<DNA-1MB>

80 parts by weight of talc and 20 parts by weight of DNA-1 wereuniformly mixed by Henschel mixer to prepare a powdery masterbatch.

Reference Example 6 [Masterbatch of radical initiator]

<PO-1MB>

A propylene homopolymer on which 8 parts by weight of1,3-bis(t-butylperoxypropyl)benzene (SANPEROX® -TY1.3 manufactured bySanken Kako Co.) as an organic peroxide as radical initiators wassupported was used.

Examples and comparative examples were carried out by using thematerials of Reference Examples 1-6 as starting materials. Compositionsare shown in Tables 1 and 3 and properties of the correspondingcompositions are shown in Tables 2 and 4. Regarding compositions shownin Table 1, the polyolefin-resin (A), the polyphenylene-ether-resin (B),and the rubber-like material (C) are shown by % by weight so thatamounts of them total to 100% by weight. Amounts of the other componentsare shown by part by weight based on 100 parts by weight of the abovetotal amount of polymers.

EXAMPLE 1

PP-1 (5.6 kg), PPE-1 (3.0 kg), El? R-1 (1.4 kg), maleic anhydride (0.15kg), styrene (0.2 kg), and PO-1MB (0.12 kg) were uniformly mixed by aHenschel mixer. Then, the mixture was fed to a twin-screw kneadingmachine TEX 44 SS-30BW-2V manufactured by Nippon Seikosho K. K. set at240° C. from the first feed opening and was melt kneaded. Then, DNA-1(0.2 kg) was fed from the second feed opening in a constant amount usinga micropump KHD-W-294 manufactured by Kyowa Seimitsu Co. and athermoplastic resin composition was produced at an extrusion amount of30 kg under suction from a vent. Feed composition ratio is shown inTable 1. From this composition, test pieces were prepared under givenmolding conditions and were subjected to evaluation of properties bygiven evaluation methods. Results of evaluation are shown in Table 2.

COMPARATIVE EXAMPLE 1

A composition was produced in the same manner as in Example 1 exceptthat DNA-1 was not used. Test pieces were prepared therefrom under givenmolding conditions and subjected to evaluation of properties by givenmethods. The results are shown in Table 2. It can be seen that thethermoplastic resin composition of Example 1 of the present inventionwas remarkably improved in Izod impact strength and heat distortiontemperature as compared with the composition of Comparative Example 1where DNA-1 was not used as dinitrodiamines.

EXAMPLE 2

PP-1 (3.0 kg), PPE-1 (1.0 kg), EPR-1 (2.2 kg), SEP-1 (0.1 kg) , maleicanhydride (0.15 kg) , styrene (0.2 kg), and PO-1MB (0.12 kg) wereuniformly mixed by a Henschel mixer and fed from the first feed openingand melt kneaded as in Example 1. Then, PP-2 (3.7 kg) and DNA-1MB (0.5kg) were fed from the second feed opening in a constant amount and athermoplastic resin composition was produced in the same manner as inExample 1. Feed composition ratio is shown in Table 1. Test pieces wereprepared therefrom under given molding conditions and were subjected toevaluation of properties by given methods. The evaluation results areshown in Table 2.

COMPARATIVE EXAMPLE 2

Example 2 was repeated except that DNA-1MB was not used. Test pieceswere prepared under given molding conditions and subjected to evaluationof properties by given methods. The results are shown in Tables 1 and 2.

It can be seen that the thermoplastic resin composition of Example 2 ofthe present invention was markedly improved in Izod impact strength andheat distortion temperature as compared with the composition ofComparative Example 2 where dinitrodiamine was not used.

EXAMPLE 3

A thermoplastic resin composition was obtained in the same manner as inExample 2 except that amount of PP-1 was 2.0 kg and that of PPE-1 was2.0 kg. Test pieces were prepared therefrom under given moldingconditions and were subjected to evaluation of properties by givenmethods. The results are shown in Tables 1 and 2.

COMPARATIVE EXAMPLE 3

A composition was produced in the same manner as in Example 3 exceptthat DNA-1MB was not used. Test pieces were prepared therefrom undergiven molding conditions and subjected to evaluation of properties bygiven methods. The results are shown in Tables 1 and 2.

It can be seen that the thermoplastic resin composition of Example 3 ofthe present invention was much improved in Izod impact strength and heatdistortion temperature as compared with the composition of ComparativeExample 3 where dinitrodiamine was not used.

EXAMPLE 4

A thermoplastic resin composition was obtained in the same manner as inExample 3 except that amount of EPR-1 was 2.1 kg and that of SEP-1 was0.2 kg. Test pieces were prepared therefrom under given moldingConditions and were subjected to evaluation of properties by givenmethods. The results are shown in Tables 1 and 2.

COMPARATIVE EXAMPLE 4

A composition was obtained in the same manner as in Example 4 exceptthat DNA-1MB was not used. Test pieces were prepared under given moldingconditions and subjected to evaluation of properties by given methods.The results are shown in Tables 1 and 2.

It can be seen that the thermoplastic resin composition of Example 4 ofthe present invention were uniformly mixed at the ratio as shown inTable 3 by a Henschel mixer and was fed from the first feed opening at atime and thermoplastic resin compositions of the present invention wasproduced under given conditions.

In Comparative Examples 5-7, compositions were produced in the samemanner as in Examples 6-10 except that dinitrodiamine (D) was not used.

Test pieces were prepared under given molding conditions and evaluationof properties were conducted by given methods in Examples 6-10 andComparative Examples 5-7. Results of evaluation of properties are shownin Table 4.

When comparison is made between Examples 6 and 7 and Comparative Example5, Example 8 and Comparative Example 6, and Example 10 and ComparativeExample 7, it can be seen that tensile characteristics of thermoplasticresin compositions of Examples of the present invention in whichdinitrodiamine (D) was added was extremely superior.

EXAMPLE 11

First, a thermoplastic resin composition was produced frompolyolefin-resin (A), polyphenylene-ether-resin (B), and dinitrodiamine(D) at the ratio shown in Table 3 in the same manner as in Examples 6-10and then, this thermoplastic resin composition was uniformly mixed withpolyolefin at the ratio shown in Table 3 by a Henschel mixer. Themixture was fed from the first feed opening at a time and athermoplastic resin composition of the present invention was producedunder given conditions. was markedly improved in Izod impact strengthand heat distortion temperature as compared with the composition ofComparative Example 4 where dinitrodiamine was not used.

EXAMPLE 5

A thermoplastic resin composition was produced at the same compositionas in Example 2 by changing the process for production.

PP-1 (3.0 kg), PPE-1 (1.0 kg), EPR-1 (2.2 kg), SEP-1 (0.1 kg), maleicanhydride (0.15 kg), styrene (0.2 kg), and PO-1MB (0.12 kg) wereuniformly mixed by a Henschel mixer and the mixture was fed to the firstfeed opening and DNA-1MB (0.5 kg) was fed to the second feed opening inconstant amounts and a thermoplastic resin composition was produced at atotal extrusion amount of 30 kg/hour under suction from a vent. Thisthermoplastic resin composition (7.27 kg) and PP-2 (3.7 kg) wereuniformly mixed by a Henschel mixer and the mixture was fed from thefirst feed opening at a time and the desired thermoplastic resincomposition was produced under given conditions. Test pieces wereprepared therefrom under given molding conditions and were subjected toevaluation of properties by given evaluation methods. The results areshown in Tables 1 and 2.

This thermoplastic resin composition had nearly the same good propertiesas that of Example 2.

EXAMPLES 6-10 AND COMPARATIVE EXAMPLES 5-7

In Examples 6-10, polyolefin-resin (A), polyphenylene-ether-resin (B),and dinitrodiamine (D)

Test pieces were prepared under given molding conditions and evaluationof properties was conducted by given evaluation methods. The results areshown in Table 4.

The thermoplastic resin composition of Example 11 of the presentinvention was much superior in tensile characteristics to thecomposition of Comparative Example 7 and besides was equal or superiorin flowability as shown by melt flow rate.

                                      TABLE 1                                     __________________________________________________________________________           Component                                                                                                           Radical                                                                             Dinitro-                          Polyolefin-                                                                          Polyphenylene-                                                                        Rubber-like                                                                             Maleic Styrene                                                                             initiator                                                                           diamines                          resin (A)                                                                            ether-resin (B)                                                                       material (C)                                                                            anhydride (F)                                                                        (N)   (PO-1MB)                                                                            (D)   Polyolefin                  (wt %)                   (part by weight)                                                              part by weight based on                              (R-2)                    100 parts by weight of (R-2)                                                                     part by weight based                                                          on 100 parts by            No.    (R-4)                                       weight of                  __________________________________________________________________________                                                       (R-2)                      Example 1                                                                            PP-1   PPE-1   EPR-1     1.5    2.0   1.2   DNA-1 --                          56     30      14                           1.9                        Example 2                                                                            PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   DNA-1MB                                                                             PP-2                        47.6   15.9    34.9 1.6                     7.9   63.1                 Example 3                                                                            PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   DNA-1MB                                                                             PP-2                        31.7   31.7    35.0 1.6                     7.9   63.1                 Example 4                                                                            PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   DNA-1MB                                                                             PP-2                        31.7   31.7    33.4 3.1                     7.9   63.1                 Example 5                                                                            PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   DNA-1MB                                                                             PP-2                        47.6   15.9    34.9 1.6                     7.9   63.1                 Comparative                                                                          PP-1   PPE-1   EPR-1     1.5    2.0   1.2   --    --                   Example 1                                                                            56     30      14                                                      Comparative                                                                          PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   --    PP-2                 Example 2                                                                            47.6   15.9    34.9 1.6                           63.1                 Comparative                                                                          PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   --    PP-2                 Example 3                                                                            31.7   31.7    35.0 1.6                           63.1                 Comparative                                                                          PP-1   PPE-1   EPR-1                                                                              SEP-1                                                                              2.4    3.2   1.9   --    PP-2                 Example 4                                                                            31.4   31.7    33.4 3.2                           63.1                 __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                                                   Penetration                                 Tensile        Flexural  Izod impact                                                                            impact stength                        Melt flow                                                                           properties     properties                                                                              strength (YE/ET) Heat distortion               rate  Yield strength                                                                        Elongation at                                                                        Modulus                                                                            Strength                                                                           23° C.                                                                     -30° C.                                                                     -30° C.                                                                        temperature                   (g/10 min)                                                                          (kg/cm.sup.2)                                                                         break (%)                                                                            (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (kg · cm/cm)                                                                  (J: Joule)                                                                            (° C.)          __________________________________________________________________________    Example 1                                                                            0.8   214      30    13200                                                                              409  8.9 2.5  1.7/3.3                                                                           (B) 158                    Example 2                                                                            2.3   174     460    9700 207  90  20.0 25/39                                                                             (D) 103                    Example 3                                                                            2.0   177     135    9600 216  45.7                                                                              9.5  24/37                                                                             (D˜B)                                                                       118                    Example 4                                                                            1.2   168     130    8800 210  59  30.0 26/40                                                                             (D) 108                    Example 5                                                                            2.2   170     500    9600 200  95  25.0 27/42                                                                             (D) 100                    Comparative                                                                          6.3   214      8     11800                                                                              313  1.8 1.2  0.7/2.3                                                                           (B) 126                    Example 1                                                                     Comparative                                                                          15.0  175      90    8700 160  18.2                                                                              9.7  10/12                                                                             (B)  95                    Example 2                                                                     Comparative                                                                          12.5  180      36    8600 170  9.2 5.0  9/11                                                                              (B) 100                    Example 3                                                                     Comparative                                                                          7.5   160      40    7900 160  11.9                                                                              6.5  11/13                                                                             (B)  96                    Example 4                                                                     __________________________________________________________________________     Notes)                                                                        *1 faicial impact strength; YE: Yield point energy; TE: Total energy; (D)     and (B): Fracture states; (D): Ductile fracture; (B): Brittle fracture.  

                  TABLE 3                                                         ______________________________________                                               Component                                                                     Polyolefin-                                                                           Polyphenylene-                                                                            Dinitro-                                                  resin   ether-resin Poly-    diamines                                         (A)     (B)         olefin   (D)                                              ratio                                                                                                  (parts by                                     No.      (wt %)                 weight)                                       ______________________________________                                        Example 6                                                                              PP-3      PPE-1       --     DNA-1                                            50        50                 2                                       Example 7                                                                              PP-3      PPE-1       --     DNA-1                                            50        5                  5                                       Example 8                                                                              M-PP-1    PPE-1       --     DNA-1                                            50        50                 2                                       Example 9                                                                              M-PP-1    PPE-1       --     DNA-1                                            70        30                 2                                       Example 10                                                                             M-PP-1    PPE-1       --     DNA-1                                            30        70                 2                                       Example 11                                                                             M-PP-1    PPE-1       PP-4   DNA-1                                            40        30          30     2                                       Comparative                                                                            PP-3      PPE-1       --     --                                      Example 5                                                                              50        50                                                         Comparative                                                                            M-PP-1    PPE-1       --     --                                      Example 6                                                                              50        50                                                         Comparative                                                                            M-PP-1    PPE-1       --     --                                      Example 7                                                                              30                                                                   ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                Properties                                                                    Melt flow                                                                             Tensile properties                                                      rate      Yield strength                                                                              Elongation at                               No.       (g/10 min)                                                                              (kg/cm.sup.2) break (%)                                   ______________________________________                                        Example 6 3.3       460           24                                          Example 7 4.5       460           24                                          Example 8 11        340           15                                          Example 9 16        320           18                                          Example 10                                                                              4.3       360           12                                          Example 11                                                                              55        350           13                                          Comparative                                                                             4.0       440           19                                          Example 5                                                                     Comparative                                                                             26        200           9                                           Example 6                                                                     Comparative                                                                             50        180           12                                          Example 7                                                                     ______________________________________                                    

Industrial Applicability

As explained above, according to the present invention, a thermoplasticresin composition can be provided which is excellent in compatibilitybetween polyolefin and polyphenylene ether, in balance of mechanicalproperties such as impact strength and heat resistance, and in solventresistance.

The novel thermoplastic resin composition provided by the presentinvention can be easily processed into shaped articles, film sheets, andthe like by processing methods normally used for thermoplastic resincompositions such as injection molding and extrusion molding and canafford articles which are markedly excellent in balance of stiffness,heat resistance, impact resistance, scratchability, paintability, oilresistance, chemical resistance, and water resistance and superior inuniformity of appearance and smoothness. The articles are suitablyemployed for uses which require heat resistance and impact resistance,especially impact resistance at low temperatures of markedly high level.

We claim:
 1. A thermoplastic resin composition, comprising:100 parts byweight of (R-1); and 0.001-10 parts by weight of a dinitrodiamine (D)per 100 parts by weight of (A)+(B) , wherein the dinitrodiamine (D) isrepresented by the formula (I): ##STR12## wherein X represents one of adivalent chain aliphatic group, a cyclic aliphatic group, an aromaticgroup, and an aromatic group containing one of a halogen or oxygen, R¹represents one of a hydrogen atom, a chain aliphatic group, a cyclicaliphatic group or an aromatic group, with the proviso that when boththe X and R¹ are chain aliphatic groups, nitrogen atoms may further bondto each other to form a heterocyclic ring through X and R¹, R² and R₃are independently one of a hydrogen atom and an alkyl group of 1-12carbon atoms, and R² and R³ may bond to wherein (R-1) is obtained bymelt-kneading a composition consisting essentially of: 9- 5% by weightof a polyolefin-resin (A) based on the total weight of (A)+(B), saidpolyolefin-resin (A) is at least one member selected from the groupconsisting of polyolefins selected from homopolymers of one of ethyleneand α-olefin and copolymers of two or more of ethylene and α-olefin, andmodified polyolefins obtained by modifying said polyolefins with amodifier, wherein said modifier is at least one member selected frompolyfunctional compounds (E) having at least one of a carboxylic acidgroup, an acid anhydride group, an acid amide group, an imide group, acarboxylic acid ester group, an epoxy group, an amino group and ahydroxyl group and unsaturated monomers (L) other than thepolyfunctional compounds (E); and 5-95% by weight of apoly-phenylene-ether-resin (B) based on the total weight of (A)+(B),said poly-phenylene-ether-resin (B) is at least one member selected fromthe group consisting of polyphenylene ethers, modified polyphenyleneethers obtained by modifying said polyphenylene ethers with saidmodifiers, (E) and/or (L), compositions comprising a polyphenylene etherand at least one aromatic vinyl polymer resin (M) selected from thegroup consisting of an aromatic vinyl polymer, a copolymer of anaromatic vinyl compound with another monomer and a rubber-modifiedaromatic vinyl polymer and compositions comprising said modifiedpolyphenylene ethers and at least one aromatic vinyl polymer resin (M);and 0.01-20 parts by weight of the polyfunctional compound (E) and/orthe unsaturated monomer (L) per 100 parts by weight of (A)+(B) , andoptionally 0.001-10 parts by weight of a radical initiator per 100 partsby weight of (A)+(B).
 2. A thermoplastic resin composition whichcomprises 100 parts by weight of the composition (R-1) defined in claim1, 0.001-10 parts by weight of a dinitrodiamine (D) per 100 parts byweight of (A)+(B), and 1-1800 parts by weight of an additionalpolyolefin per 100 parts by weight of (A)+(B), and optionally 1-100parts by weight of an elastomeric polymer per 100 parts by weight of(A)+(B), and wherein the amount of the additional polyolefin is lessthan 95% by weight based on the total amount of the additionalpolyolefin and the polyolefin-resin (A) of the composition (R-1).
 3. Athermoplastic resin composition comprising:(R-2) is obtained bymelt-kneading: 100 parts by weight of (R-2) wherein (R-2) is obtained bymelt-kneading: 94-2% by weight of a polyolefin-resin (A) based on thetotal weight of (A)+(B)+(C), wherein said polyolefin-resin (A) is atleast one member selected from the group consisting of polyolefinsselected from homopolymers of one of ethylene and α-olefin andcopolymers of two or more of ethylene and α-olefin, and modifiedpolyolefins obtained by modifying said polyolefins with a modifier,wherein said modifier is at least one member selected frompolyfunctional compounds (E) having at least one of a carboxylic acidgroup, an acid anhydride group, an acid amide group, an imide group, acarboxylic acid ester group, an epoxy group, an amino group and ahydroxyl group and unsaturated monomers (L) other than thepolyfunctional compounds (E); 2-94% by weight of apolyphenylene-ether-resin (B) based on the total weight of (A)+(B)+(C),wherein said polyphenylene-ether-resin (B) is at least one memberselected from the group consisting of polyphenylene ethers, modifiedpolyphenylene ethers obtained by modifying said polyphenylene etherswith said modifiers (E) and/or (L), compositions comprising apolyphenylene ether and at least one aromatic vinyl polymer resin (M)selected from the group consisting of an aromatic vinyl polymer, acopolymer of an aromatic vinyl compound with another monomer and arubber-modified aromatic vinyl polymer and compositions comprising saidmodified polyphenylene ethers and at least one aromatic vinyl polymerresin (M); 1-50% by weight of a rubber material (C) based on the totalweight of (A)+(B)+(C), said material (C) is at least one materialselected from the group consisting of natural or synthetic elastomericpolymers which are elastic at 20°-25° C. and modified elastomericpolymers obtained by modifying said elastomeric polymers with saidmodifier; 0.01-20 parts by weight of the polyfunctional compound (E)and/or the unsaturated monomer (L) per 100 parts by weight of(A)+(B)+(C), and optionally 0.001-10 parts by weight of a radicalinitiator per 100 parts by weight of (A)+(B)+(C); and 0.001-10 parts byweight of a dinitrodiamine (D) per 100 parts by weight of (A)+(B)+(C),said dinitrodiamine (D) being represented by the formula (I): ##STR13##wherein X represents one of a divalent chain aliphatic group, a cyclicaliphatic group, an aromatic group, and an aromatic group containing oneof a halogen or oxygen, R¹ represents one of a hydrogen atom, a chainaliphatic group, a cyclic aliphatic group or an aromatic group, with theproviso that when both the X and R¹ are chain aliphatic groups, nitrogenatoms may further bond to each other to form a heterocyclic ring throughX and R¹, R² and R₃ are independently one of a hydrogen atom and analkyl group of 1-12 carbon atoms, and R² and R³ may bond to form a ring.4. A thermoplastic resin composition which comprises 100 parts by weightof the composition (R-2) in claim 3, 0.001-10 parts by weight of adinitrodiamine (D) per 100 parts by weight of (A)+(B)+(C) and 1-1800parts by weight of an additional polyolefin per 100 parts by weight of(A)+(B)+(C), and optionally 1-100 parts by weight of an elastomericpolymer per 100 parts by weight of (A)+(B)+(C), wherein an amount of theadditional polyolefin is less than 95% by weight based on the totalamount of the additional polyolefin and the polyolefin-resin (A) of thecomposition (R-2) and an amount of the elastomeric polymer being lessthan 95% by weight based on the total amount of the elastomeric polymerand the rubber material (C) of the composition (R-2).